Lubricants with molybdenum containing compositions and methods of using the same

ABSTRACT

This invention relates to a lubricating composition comprising a major amount of an oil of lubricating viscosity and (A) an antiwear improving amount of at least one molybdenum containing composition, and (B) at least one member selected from the group consisting of (i) at least one borated overbased metal salt of an acidic organic compound, provided that (A) and (Bi) are not the same, (ii) a combination of (a) at least one organic polysulfide or at least one ashless dithiocarbamate containing composition and (b) at least one component selected from the group consisting of a metal thiophosphate, a phosphoric acid ester or salt thereof, a phosphorus-containing carboxylic acid, ester, ether, or amide, a borated dispersant, an alkali metal borate, a borated fatty amine, a borated phospholipid, a borate ester, and mixtures thereof, and (iii) a combination of (i) and (ii).

FIELD OF THE INVENTION

[0001] This invention relates to a lubricating composition comprising amolybdenum composition which improves the antiwear properties of thelubricant. The invention also relates to methods of lubricating atransmission or differential. These lubricating compositions areparticularly useful as manual transmission fluids.

BACKGROUND OF THE INVENTION

[0002] Engine, transmission, and gear designs utilize a variety ofmetallurgy in their designs. In transmissions, often a brasssynchronizer ring is used. This brass Add synchronizer engages with asteel cone to affect changing of the transmission gears One problem,associated with this design, is brass ring wear. It is thereforedesirable to have a lubricant which reduces brass on steel wear.

[0003] Often lubricants contain mixtures of additives which are intendedto protect the engines, transmissions, and gears against wear andoxidation. Many such mixtures are known to those in the art. However, itwould be desirable to have a specific mixture of additives which alsoprovide protection against brass on steel wear.

[0004] U.S. Pat. Nos. 3,541,014 (LeSuer), and 5,143,633 (Gallo et al)describe various molybdenum containing overbased metal salts.

[0005] U.S. Pat. Nos. 3,446,735 (Wiese), 4,289,635 (Schroeck), 4,456,538(Ripple), 4,692,256 (Umemura et al), 4,704,215 (Hata et al), and4,846,983 (Ward, Jr.) describe various molybdenum compound andcomposition either used alone or used in combination with otheradditives.

SUMMARY OF THE INVENTION

[0006] This invention relates to a lubricating composition comprising amajor e S amount of an oil of lubricating viscosity and (A) an antiwearimproving amount of at least one molybdenum containing composition, and(B) at least one member selected from the group consisting of (i) atleast one borated overbased metal salt of an acidic organic compound,provided that (A) and (Bi) are not the same, (ii) a combination of (a)at least one organic polysulfide or at least one ashless dithiocarbamatecontaining composition and (b) at least one component selected from thegroup consisting of a metal thiophosphate, a phosphoric acid ester orsalt thereof, a phosphorus-containing carboxylic acid, ester, ether, oramide, a borated dispersant, an alkali metal borate, a borated tattyamine, a borated phospholipid, a borate ester, and mixtures thereof, and(iii) a combination of (i) and (ii). The lubricating, compositions haveimproved antiwear properties. When the lubricating composition is usedin a manual transmission, the amount of brass on steel wear is reduced.

DESCRIPTION OF THE INVENTION

[0007] The term “hydrocarbyl” includes hydrocarbon as well assubstantially hydrocarbon groups. Substantially hydrocarbon describesgroups which contain heteroatom substituents which do not alter thepredominantly hydrocarbon nature of the group. Examples of hydrocarbylgroups include the following:

[0008] (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl oralkenyl). alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents,aromatic-, aliphatic- and alicyclic-substituted aromatic substituentsand the like as well as cyclic substituents wherein the ring iscompleted through another portion of the molecule (that is, for example,any two indicated substituents may together form an alicyclic radical).

[0009] (2) substituted hydrocarbon substituents, i.e, those substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent; those skilled in the art will be aware of such groups(e.g., halo (especially chloro and fluoro), hydroxy, mercapto, nitro,nitroso, sulfoxy, etc.);

[0010] (3) heteroatom substituents, i.e., substituents which will, whilehaving a predominantly hydrocarbon character within the context of thisinvention, contain an atom other than carbon present in a ring or chainotherwise composed of carbon atoms (e.g., alkoxy or alkylthio). Suitableheteroatoms will be apparent to those of ordinary skill in the art andinclude, for example, sulfur, oxygen, nitrogen and such substituents as,e.g., pyridyl, furyl, thienyl, imidazolyl, etc.

[0011] In general, no more than about 2, preferably no more than one,hetero substituent will be present for every ten carbon atoms in thehydrocarbyl group. Typically, there will be no such hetero atomsubstituents in the hydrocarbyl group. Therefore, the hydrocarbyl groupis purely hydrocarbon.

[0012] In the specification and claims, the term “lubricatingcomposition” refers to the combination of an oil of lubricatingviscosity and additives. The percentages by weight are based on theamount of total amount of the additive and the oil of lubricatingviscosity.

[0013] As described herein, the use of molybdenum containingcompositions in combination with specific additives improves theantiwear properties of lubricants, especially brass on steel wear. Themolybdenum composition is generally used at a level sufficient todeliver from about 125 up to about 900 ppm, preferably from about 200 upto about 800 ppm, more preferably from about 250 up to about 700 ppm ofmolybdenum metal to the lubricating composition. Here, as well aselsewhere in the specification, the ratios and range limits may becombined. The molybdenum metal is in an oil soluble or dispersible form.The molybdenum compositions include a molybdenum containing overbasedsalt of an acidic organic composition, a molybdenum thiocarbamate, and amolybdenum thiophosphate. In one embodiment, the molybdenum compositionis other than a molybdenum containing dispersant such as a molybdenumcontaining succinimide.

[0014] Molybdenum Overbased Compositions

[0015] In one embodiment, the molybdenum composition is in the form of amolybdenum overbased salt of an acidic organic compound. The molybdenumoverbased metal salts are particularly useful in lubricants whichrequire thermal stability. The molybdenum containing overbased salts arecharacterized by a metal content in excess of that which would bepresent according to the stoichiometry of the metal and the particularorganic compound reacted with the metal. The amount of excess metal iscommonly expressed in terms of metal ratio. The term “metal ratio” isthe ratio of the total equivalents of the metal to the equivalents ofthe acidic organic compound. A salt having 4.5 times as much metal aspresent in a normal salt will have metal excess of 3.5 equivalents perequivalents of organic acid or a ratio of 4.5. The molybdenum containingoverbased salts preferably have a metal ratio from about 1.5, or fromabout 3. The molybdenum containing overbased salts generally have ametal ratio up to about 40, or up to about 30, or up to about 25. In oneembodiment, the metal salts have a metal ratio from about 10, preferablyfrom about 12 up to about 40, or up to about 30.

[0016] The molybdenum containing overbased salts additionally maycontain an alkali or alkaline earth metal. Examples of such metalsinclude sodium, potassium, lithium, magnesium, calcium, barium,titanium, manganese, cobalt, nickel, copper, and zinc, preferablysodium, potassium, calcium, and magnesium. The alkali or alkaline earthmetal may typically be present in an amount from about 2% up to about20%, or from about 4% up to about 18%, or from about 6 to about 14% byweight of the molybdenum containing overbased salts.

[0017] The acidic organic compounds used to prepare the molybdenumcontaining overbased metal salts are generally selected from the groupconsisting of sulfonic acids, carboxylic acids, phosphorus acids,phenols, and derivatives thereof. Preferably, the overbased materialsare prepared from sulfonic acids, carboxylic acids, or derivatives ofthese acids, such as esters, anhydrides, etc. The sulfonic acids arepreferably mono-, di-, and tri-aliphatic hydrocarbon-substitutedaromatic sulfonic acids. The hydrocarbon-substituent may be derived froma polyalkene. The polyalkenes include homopolymers and interpolymers ofpolymerizable olefin monomers having from 2 up to about 16, preferablyfrom 2 to about 8, more preferably from 2 to about 4 carbon atoms. Theolefins may be monoolefins, such as ethylene, propylene, 1-butene,isobutene, and 1-octene, or a polyolefinic monomer, such as1,3-butadiene and isoprene. In one embodiment, the interpolymer is ahomopolymer. An example of a preferred homopolymer is a polybutene,preferably a polybutene in which about 50% of the polymer is derivedfrom isobutylene. The polyalkenes are prepared by conventionalprocedures.

[0018] The polyalkene is generally characterized as containing from atleast about 8, or at least about 15, or at least about 20 carbon atoms.The polyalkene generally contains up to about 40 carbon atoms, or up toabout 30 carbon atoms. In one embodiment, the polyalkenes have a{overscore (M)}n from about 250, or from about 300 up to about 600, orup to about 500, or up to about 400. The abbreviation {overscore (M)}nis the conventional symbol representing number average molecular weight.Gel permeation chromatography (GPC) is a method which provides bothweight average and number average molecular weights as well as theentire molecular weight distribution of the polymers. For purpose ofthis invention a series of fractionated polymers of isobutene,polyisobutene, is used as the calibration standard in the GPC.

[0019] Examples of sulfonic acids include mahogany sulfonic acids,bright stock sultonic acids, petroleum sulfonic acids, mono- andpolywax-substituted naphthalene sulfonic acids, saturated,hydroxy-substituted, and unsaturated paraffin wax sulfonic acids,wax-substituted benzene or naphthalene sulfonic acids, tetraisobutylenesulfonic acids, tetra-amylene sulfonic acids, dodecylbenzene sulfonicacids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonic acids,sulfonic acids derived by the treatment of at least one of theabove-described polyalkenes (preferably polybutene) with chlorosulfonicacid, and the like.

[0020] The sulfonic acids include dodecyl benzene “bottoms” sulfonicacids. Dodecyl benzene bottoms, principally mixtures of mono- anddi-dodecyl benzenes, are available as by-products from the manufactureof household detergents. Similar products obtained from alkylationbottoms formed during manufacture of linear alkyl sulfonates (LAS) arealso useful in making the sulfonates used in this invention. Theproduction of sulfonic acids is well known to those skilled in the art.See, for example, the article “Sulfonates” in Kirk-Othmer “Encyclopediaof Chemical Technology”, Second Edition, Vol. 19, pp. 291 et seq.published by John Wiley & Sons, N.Y. (1969).

[0021] In one embodiment, the acidic organic compound may be acarboxylic acid, or derivative thereof. Suitable carboxylic acidsinclude aliphatic, cycloaliphatic, and aromatic mono- and polybasiccarboxylic acids. In one embodiment, the carboxylic acid, or derivativethereof, is an aliphatic acid, or derivative thereof, containing fromabout 8, or from about 12. The carboxylic acid or derivative thereofgenerally contains up to about 50, or up to about 25 carbon atoms.Illustrative carboxylic acids and derivatives thereof include2-ethylhexanoic acid, palmitic acid, stearic acid, oleic acid, linoleicacid, behenic acid, octadecyl-substituted adipic acid, stearyl-benzoicacid, polybutenyl substituted succinic acid or anhydride derived frompolybutene ({overscore (M)}n is from about 200-1500, preferably fromabout 300-1500, more preferably from about 800-1200), polypropylenesubstituted succinic acid or anhydride derived from polypropene({overscore (M)}n is from about 200-2000, preferably from about300-1500, more preferably from about 800-1200), acids formed byoxidation of petrolatum or of hydrocarbon waxes, commercially availablemixtures of two or more carboxylic acids, such as tall oil acids androsin acids, and mixtures of the above acids, and/or their derivatives.

[0022] In one embodiment, the carboxylic acid or derivative thereof is ahydrocarbyl-substituted carboxylic acylating agent. The acylating agentincludes halides, esters, anhydrides, etc., preferably acid, esters, oranhydrides, more preferably anhydrides. Preferably the carboxylicacylating agent is a succinic acylating agent. The acylating agent mayhe derived from a monocarboxylic or a polycarboxylic acylating agent andone or more of the above described polyalkenes. In one embodiment, thepolyalkene is characterized by an {overscore (M)}n of at least about400, or at least about 500. Generally, the polyalkene is characterizedby an {overscore (M)}n from about 500 up to about 5000, or from about700 up to about 2500, or from about 800 up to about 2000, or from about900 up to about 1500. In one embodiment, the hydrocarbyl group of thecarboxylic acylating agent has a {overscore (M)}n from about 400 toabout 1200, preferably from about 400 to about 800.

[0023] In another embodiment, the hydrocarbyl group is derived frompolyalkenes having an {overscore (M)}n from about 1300 up to about 5000,and the {overscore (M)}w/{overscore (M)}n value is from about 1.5 up toabout 4, or from about 1.8 to about 3.6, or from about 2.5 to about 3.2.The hydrocarbyl-substituted carboxylic acylating agents are prepared byknown procedures. In another embodiment, the acylating agents areprepared by reacting the above described polyalkenes with an excess ofmaleic anhydride to provide substituted succinic acylating agentswherein the number of succinic groups for each equivalent weight ofsubstituent group is from about 1.3 to about 4.5 succinic groups perequivalent weight of substituent groups. A suitable range is from about1.4 up to 3.5, or from about 1.5 up to about 2.5 succinic groups perequivalent weight of substituent groups. In this embodiment, thepolyalkene has an {overscore (M)}n from about 1300 to about 5000. A morepreferred range for {overscore (M)}n is from about 1500 to about 2800,and a most preferred range of {overscore (M)}n is from about 1500 toabout 2400.

[0024] Carboxylic acids or derivatives thereof (e.g. acylating agents)and their preparation are described in U.S. Pat. Nos. 3,215,707 (Rense);3,219,666 (Norman et al); 3,231,587 (Rense); 3,912,764 (Palmer);4,110,349 (Cohen); and 4,234,435 (Meinhardt et al); and U.K. 1,440,219.The disclosures of these patents are hereby incorporated by reference.

[0025] In another embodiment, the acidic organic compound is analkyloxyalkylene-acetic acid or alkylphenoxy-acetic acid, morepreferably alkylpoly-oxyalkylene-acetic acid or derivatives thereof.Some specific examples of these compounds include:iso-stearylpentaethyleneglycolacetic acid;iso-stearyl-O—(CH₂CH₂O)₅CH₂CO₂Na; lauryl-O—(CH₂CH₂O)₂ ₅CH₂CO₂H;lauryl-O—(CH₂CH₂O)₃ ₃CH₂CO₂H; oleyl-O—(CH₂CH₂O)₄CH₂CO₂H;lauryl-O—(CH₂CH₂O)₄ ₅CH₂CO₂H; lauryl-O—(CH₂CH₂O)₁₀CH₂CO₂H;lauryl-O—(CH₂-CH₂O)₁₆CH₂CO₂H; octyl-phenyl-O—(CH₂CH₂O)₈CH₂CO₂H;octyl-phenyl-O—(CH₂CH₂O)₁₉CH₂CO₂H; 2-octyldecanyl-O—(CH₂CH₂O)₆CH₂CO₂H.These acids are available commercially from Sandoz Chemical under thetradename Sandopan acids.

[0026] In another embodiment, the acidic organic compound is an aromaticcarboxylic acid. A group of useful aromatic carboxylic acids are thoseof the formula

[0027] wherein R₁ is an aliphatic hydrocarbyl group derived from theabove-described olefins or polyalkenes, a is a number in the range of 1to about 4, usually 1 or 2, Ar is an aromatic group, each X isindependently sulfur or oxygen, preferably oxygen, b is a number in therange from 1 to about 4, usually from 1 to 2, c is a number in the rangeof zero to about 4, usually 1 to 2, with the proviso that the sum of a,b, and c does not exceed the number of valences of Ar. Examples ofaromatic acids include substituted benzoic, phthalic, and salicylicacids. The R₁ group is a hydrocarbyl group that is directly bonded tothe aromatic group Ar. Examples of R₁ groups include substituentsderived from the above described polyalkenes.

[0028] Ar may be mono- or polynuclear. Mononuclear groups include aphenyl, a pyridyl, or a thienyl. The polynuclear groups may be of thefused type wherein an aromatic nucleus is fused at two points to anothernucleus such as found in naphthyl, anthranyl, etc. The polynuclear groupcan also be of the linked type are linked through bridging linkages suchas alkylene, ether, keto, sulfide disulfide, and polysulfide, containing3 to about 6 sulfur atoms, linkages. Examples of the aromatic groupsinclude phenyl, phenylene, and naphthalenyl groups.

[0029] In one embodiment, the carboxylic acid or derivative thereof is asalicylic acid or derivative thereof. Preferably the salicylic acid orderivative thereof is an aliphatic hydrocarbon-substituted salicylicacid or derivative thereof. The hydrocarbon substituent is generallyderived from one or more of the above described polyalkenes.

[0030] The above aromatic carboxylic acids are known or can be preparedaccording to procedures known in the art. Carboxylic acids of the typeillustrated by these formulae and processes for preparing their neutraland basic metal salts are well known and disclosed, for example, in U.S.Pat. Nos. 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092;3,410,798; and 3,595,791. These patents are incorporated by referencefor their disclosure of aromatic carboxylic acids, salts thereof andmethods of making the same.

[0031] In another embodiment, the acidic organic compound is aphosphorus-containing acid, or derivative thereof. Thephosphorus-containing acids, or derivatives thereof, include phosphorusacids, such as phosphoric acid or esters; and thiophosphorus acids oresters, including mono and dithiophosphorus acids or esters. In oneembodiment, the phosphorus-containing acid is the reaction product ofone or more or the above polyalkenes and a phosphorus sulfide. Usefulphosphorus sulfides, include phosphorus pentasulfide, phosphorussesquisulfide, phosphorus heptasulfide and the like. The reaction of thepolyalkene and the phosphorus sulfide generally may occur by simplymixing the two at a temperature above 80° C., usually between 100° C.and 300° C. Generally, the products have a phosphorus content from about0.05% to about 10%, preferably from about 0.1%Y to about 5%. Therelative proportions of the phosphorizing agent t the olefin polymer isgenerally from 0.1 part to 50 parts of the phosphorus sulfide per 100parts of the polyalkene. The phosphorus-containing acids are describedin U.S. Pat. No. 3,232,883 issued to LeSuer. This reference is hereinincorporated by reference for its disclosure to thephosphorus-containing acids and methods for preparing the same.

[0032] In another embodiment, the acidic organic compound is a phenol.The phenols may be represented by the formula (R₁)_(a)—Ar—(OH)_(b),wherein R₁ is defined above for the aromatic carboxylic acids; Ar is anaromatic group, as defined above; a and b are independently numbers ofat least one, the sum of a and b being in the range of two up to thetotal number of displacable hydrogens on the aromatic nucleus or nucleiof Ar. Preferably, a and b are independently numbers in the range of 1to about 4, or to about 2. In one embodiment, R₁ and a are such thatthere is an average of at least about 8 aliphatic carbon atoms providedby the R₁ groups for each phenol compound.

[0033] In another embodiment, the molybdenum containing overbased metalsalts are borated molybdenum containing overbased metal salts. Themolybdenum containing borated overbased metal salts are prepared byreacting one of the below described borated overbased metal salts with amolybdenum containing anion. Alternatively, the molybdenum containingborated overbased metal salts may be prepared by incorporating the boroncompound into the initial reaction mixture used to make the molybdenumcontaining metal salts.

[0034] Preparation of the Molybdenum Containing Overbased Composition

[0035] In one embodiment, the molybdenum containing overbasedcompositions are prepared by reacting molybdenum containing anions withan alkali or alkaline earth metal overbased salt of an acidic organiccompound. The alkali or alkaline earth metal salts are prepared byreacting an acidic material, described below (typically carbon dioxide),with a mixture comprising an acidic organic compound. such as thosedescribed above, a reaction medium comprising at least one inert,organic solvent for the organic material, a stoichiometric excess of thealkali or alkaline earth basic metal compound, typically a metalhydroxide or oxide, and a promoter, including alcoholic and phenolicpromoters, such as alcohols having about one to about 12 carbon atoms(such as methanol, ethanol, amyl alcohol, octanol, isopropanol, andmixtures of these), and alkylated phenols (such as heptylphenols,octylphenols, and nonylphenols).

[0036] Illustrative of alkali or alkaline earth basic metal compoundsinclude hydroxides, oxides, alkoxides (typically those in which thealkoxy group contains up to 10 and preferably up to 7 carbon atoms),hydrides and amides of alkali or alkaline earth metals. Useful basicmetal compounds include lithium hydroxide, sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium hydroxide, calcium oxide, and bariumhydroxide. The alkali and alkaline earth metal salts and methods ofmaking the same are described in U.S Pat. No. 4,627,928. This patent ishereby incorporated by reference for such disclosure. A comprehensivediscussion of suitable promoters is found in U.S. Pat. Nos. 2,777,874;2,695,910; 2,616,904; 3,384,586; and 3,492,231. These patents areincorporated by reference for their disclosure of promoters.

[0037] The temperature at which the acidic material is contacted withthe remainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about 80° C. to about 300° C. and preferably from about 100°C. to about 200° C. When an alcohol or mercaptan is used as thepromoting agent, the temperature usually will not exceed the refluxtemperature of the reaction mixture.

[0038] Acidic materials, which are reacted with the mixture of theacidic organic compound, the promoter, the metal compound and thereactive medium, are also disclosed in the above cited patents, forexample, U.S. Pat. No. 2,616,904. Included within the known group ofuseful acidic materials are formic acid, acetic acid, nitric acid, boricacid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid,substituted carbamic acids, etc. Acetic acid is a very useful acidicmaterial. Inorganic acidic compounds such as HCl, SO₂, SO₃, CO₂, H₂S,N₂O₃, etc., may also he employed as the acidic materials. Preferredacidic materials are SO₂, SO₃, carbon dioxide and acetic acid, morepreferably carbon dioxide.

[0039] The methods for preparing the overbased materials are well knownin the prior art and are disclosed, for example, in the following U.S.Pat. Nos.: 2,616,904; 2,616,905; 2,616,906; 3,242,080; 3,250,710;3,256,186; 3,274,135; 3,492,231; and 4,230,586. These patents discloseprocesses, materials which can be overbased, suitable metal bases,promoters, and acidic materials. These patents are incorporated hereinby reference for these disclosures. Other descriptions of basic msulfonate salts and techniques for making them can be found in thefollowing U.S. Pat. Nos.: 2,174,110; 2,202,781; 2,239,974; 2,319,121;2,337,552; 3,488,284; 3,595,790; and 3,798,012. These are herebyincorporated by reference for their disclosures in this regard.

[0040] As described above the alkali or alkaline earth overbasedcompositions may be reacted with molybdenum containing anions to formthe molybdenum containing overbased metal salts of acidic organiccompounds. The molybdenum anions are delivered as molybdic acid orammonium or alkali metal salts of molybdic acid including (NH₄)₆ Mo₇O₂₄, (NH₄)₂ Mo₂ O₇ and various hydrates, such as (NH₄)₆ Mo₇ O₂₄ 4H₂O. Inone embodiment, the reaction is facilitated by the use of a peptizingagent. Peptizing agents include one or more of the dispersants describedherein. This process and the molybdenum containing overbasedcompositions are described in U.S. Pat. No. 3,541,014 (LeSuer). Thispatent is incorporated by reference for this disclosure.

[0041] In another embodiment, the molybdenum containing overbasedcompositions are prepared by reacting the components used in theoverbasing process in the presence of at least one organic molybdenumcomplex. The molybdenum containing organic complex is preferably anamine-molybdenum complex, which are typically prepared by a reaction ofan acidic and organic molybdenum compound with an amine. The molybdenumcompounds include molybdic acid, alkali metal molybdates, sodiumhydrogen molybdate, ammonium molybdate, MoOCl₄, and molybdenum trioxideSodium molybdate and ammonium molybdate are preferred. Theamine-molybdenum complex is in general prepared in an aqueous medium.The amine is added to an aqueous solution of an inorganic molybdenumcompound. The reaction mixture is kept at a temperature between about20° and about 100° C., preferably between about 50° and about 90° C.,for about 0.5 to about 3 hours after the addition of the amine. Theamount of acid necessary to neutralize the reaction mixture is addedbefore or after the introduction of the amine. A strong mineral acid isused, preferably sulfuric acid. The amine-molybdenum complexprecipitates. It is recovered by filtering off, washed with water anddried, if appropriate. The complex has a solid or pasty appearance,depending on the type of amine used. Its color varies from white toblue. It is virtually insoluble or very sparingly soluble inhydrocarbons.

[0042] The atomic ratio of nitrogen to molybdenum in the complex is ingeneral from about 0.25 to about 4, preferably from about 0.5 to about2. The molybdenum content of the complex varies depending on the natureof the amine used: it is between about 10% and about 45%. Among theorganic molybdenum complexes, the complexes with oxygen-containingcompounds may also be used. The 1,2-, 1,3- and 1,4-glycols are veryparticularly suitable. Ethylene glycol and propylene glycol arepreferably used. Amongst the polyols, are glycerol andtrimethylolpropane.

[0043] Some amines, or polyamines which are alkoxylated, preferably withethylene oxide or propylene oxide, are also suitable. The derivatives ofdiethanolamine or of triethanolamine may be mentioned.

[0044] The preparation of the molybdenum containing overbasedcompositions can be carried out by heating the oxygen-containingcompound at about 90°-100° C. in the presence of a molybdenum compound,such as ammonium molybdate. The water produced by the reaction isremoved using a stream of nitrogen. The molybdenum content of thecomplexes obtained varies between about 7% and about 50% by weight,depending on the degree to which unreacted oxygen-containing compoundhas been removed.

[0045] The organic molybdenum complex can be sulfurized, for example, bythe action of hydrogen sulfide (H₂S) on a suspension of the complex inan aromatic solvent such as xylene or toluene, at a temperature ofbetween about 40° C. and about 100° C. From the introduction of hydrogensulfide, the color of the suspension changes from blue-green to orange,and then to red. The amount of hydrogen sulfide introduced is such thatthe atomic ratio of sulfur to molybdenum is between about 1 and about 3.

[0046] The overbased products containing molybdenum, obtained accordingto the invention, are clear and stable and colored brown in the case ofthe sulfonates, deep green in the case of the phenolates and black inthe case of the salicylates. The color is generally red for theoverbased detergents in the presence of a sulfurized complex. Theproportion of molybdenum incorporated in the additive is close to 100%,higher than the proportions obtained during incorporation of inorganicmolybdenum derivatives. The additive contains from about 0.1% to about10% by weight, preferably from about 1% to about 4% of molybdenum. Theoverbased additives according to the invention are soluble ordispersible in hydrocarbons. The molybdenum containing overbased saltsprepared with molybdenum amine complexes are described in U.S. Pat. No.5,143,633. This patent is incorporated by reference for its descriptionof the molybdenum containing overbased salts and methods of making thesame.

[0047] The following Examples relate to molybdenum containing overbasedcompositions and methods of making the same. In the Examples, as well aselsewhere in the specification and claims, unless the context indicatesotherwise, the parts and percentages are by weight, the temperature isdegrees Celsius, and the pressure is atmospheric. In the examples thebasicity of these overbased additives is characterized by theirneutralization number or AV (alkali value) is expressed in mg of KOH pergram of product. It is determined by titration with aid of a strong acidin accordance with the standard ASTM D-2896.

EXAMPLE M-1

[0048] (a) A solution of 41.17 g of sodium molybdate Na₂MoO₄2.H₂O in 100ml of water is prepared in a reactor fitted with a temperature controland a stirrer device. The mixture is acidified by adding 55.6 g of 30%fH₂SO₄ and then heated to 60° C. This is followed by the addition of 21 gof Dinoram C from CECA SA. Dinoram C corresponds to the formulaR—N—H—(CH₂)₃-NH₂, where R is a mixture of straight-chain saturated alkylradicals containing 60% of C₁₂, 20% of C₁₄, 10% of C₁₆ and 5% of C₁₈.The blue precipitate is recovered by filtering off and then washing withwater and with methanol before drying. Finally, 47.1 g of blue solidcontaining 32.6% of molybdenum and 4.4% of nitrogen are recovered.

[0049] (b) A reaction vessel is charged with 520 ml of xylene and 30grams of the Dinoram C/molybdenum complex from above. The mixture isstirred. Then, 131.8 g of alkyixylenesulfonic acid having C₁₆₋₁₈straight-chain alkyl chain and a molecular weight of 430 and containing96% of active substance, 168 g of diluent oil 100 Neutral solvent,113.24 g of slaked lime of 96% purity and 48 ml of methanol are added tothe mixture. After neutralization of the sulfonic acid with the lime,which, if appropriate, can be carried out by heating the reactionmixture at 60° C. for 30 minutes, 55.2 g of carbon dioxide gas are thenintroduced into the mixture which is kept at a temperature of 42° C.

[0050] After carbonation and removal of water and methanol under partialvacuum, the solid residues are removed by centrifuging. Afterevaporating off the solvent, 448 g of molybdenum-containing superbasicsulfonate are recovered; neutralization number=300, its calcium contentsis 11.7% and its molybdenum content 2.17%. It is stable on dilution inlubricant oils.

EXAMPLE M-2

[0051] (a) A dispersion of 20 g of the complex prepared in Example M-1in 200 ml of xylene is prepared in a 250 ml reactor fitted with atemperature control, a stirrer and a gas bubbling system. 6.7 g of H₂Sare injected into the dispersion kept at 80° C.; the deep red solidcollected after removal of the solvent contains 28.4% of molybdenum,3.8% of nitrogen and 23.7%o of sulfur.

[0052] (b) The procedure is as in Example M-1, but 28 g of sulphurizedDinoram C/molybdenum complex (Example M-2(a) are suspended in 520 ml ofxylene, this being, carried out before the introduction of the otherreactants. The sequence of operations is identical to that of ExampleM-1 except that the residues are removed by centrifuging. Amolybdenum-containing superbasic sulphonate is d collected; AV=304. Themolybdenum, sulphur and calcium contents are, respectively, 1.63, 3.4and 11.7%. The product obtained has a brown-red color and it is stableon dilution in lubricant oils.

EXAMPLE M-3

[0053] (a) A 2-ethylhexylamine/molybdenum complex is prepared asfollows: The procedure is as in Example M-1 but 9.9 g of 98%2-ethylhexylamine are added at 60° C. before heating and acidificationand are introduced in the course of 20 , minutes into an aqueoussolution containing 15.44 g of sodium molybdate and kept B at 60° C.After heating at 60° C. for 45 minutes, the mixture is acidified with23.1 g of 30% sulfuric acid, before washing and drying the product. Thelatter is in the a form of a white solid containing 36.8% of molybdenumand 4.38% of nitrogen.

[0054] (b) The procedure is as in Example M-1, but 28 g of the2-ethylhexylamine complex prepared in Example M-3(a) are suspended in520 ml of xylene before the introduction of the other reactants. Theprocedure is the same as in Example M-1 except that the residues areremoved by centrifuging. A brown product of AV=353 is collected. Thecalcium and molybdenum contents are, respectively, 12.2 and 1.97%. Thestability on dilution in lubricant oils is perfect.

EXAMPLE M-4

[0055] The procedure is as in Example M-1(b), but 600 milliliters ofxylene, 132 grams of didodecylbenzenesulfonic acid having a molecularweight of 520 and containing 70% of active substance 30 grams of tilecomplex prepared in Example M-1(a), 104 grams of slaked lime, 52milliliters of methanol. 4.4 milliliters of ammonia and 90 rams ofdiluent oil are introduced successively into the reactor. The productcollected is brown, clear and stable in oils. The calcium and molybdenumcontents are, respectively, 10 and 2.35%.

[0056] The procedure is as in Example M-1, but 30 grams of the complexprepared in Example M-1(a) are introduced into 520 milliliters oftoluene before the addition of other reactants. The sequence ofoperations is identical to that of Example 1 except that 52.7 grams ofCO₂ are introduced during the carbonation. After centrifuging, 448 gramsof molybdenum-containing superbaseic sulfonate are recovered, AV=298.The calcium and molybdenum contents are, respectively.

EXAMPLE M-5

[0057] The procedure is as in Example M-4, but after filtration ondiatomaceous earth, 440 grams of molybdenum-containing overbasedsulfonate of AV=292 are recovered.

EXAMPLE M-4

[0058] (a) Preparation of barium overbased amine-formaldehydecondensate: A reaction vessel is charged with 1000 parts of N-octadecylpropylenediamine, 490 parts of mineral oil, 32 parts of calcium oxide,and 143 parts of water at about 44° C. and slowly heated to 102° C.under reflux conditions over a one hour period. While maintaining themixture at 100°-105° C., 303 parts of paraformaldehyde are added to thereaction mixture over three hours. The temperature is maintained for onehour, then the temperature is increased to 150° C. over two and one halfhours. Distillate (278 parts) is removed and the residue is filtered.

[0059] A separate reaction vessel is charged with 197 parts of mineraloil and 119 parts of heptylphenol. The mixture is heated to 93-99° C.where barium hydroxide monohydrate (465 parts) is added over four hours.The reaction temperature is then increased to 150° C. where 149 parts ofthe above amine-formaldehyde product (Example M-3(a)) is added over onehalf hour. Carbon dioxide is blown subsurface into the mixture at a rateof 15 parts per hour for seven hours at 150° C. Additional mineral oil(100 parts) is added to the mixture and the mixture is blown withnitrogen subsurface for two hours at 150° C. The water content of themixture is reduced to 0.3%. The residue is filtered through diatomaceousearth and the filtrate is the desired product. The product has 36%mineral oil and 30.8%/m barium.

[0060] (b) An aqueous mixture of ammonium paramolybdate tetrahydrate.(NH₄)₆Mo₇O₂₄4H₂O, is prepared by mixing 411 grams thereof with 300 gramsof water and maintaining the temperature of the mixture at about 60° C.Four 100-gram portions of this mixture are added to 457 grams of theabove barium overbased amine aldehyde condensate (Example M-5(a)) over a3.5 hour period while maintaining the temperature of the reaction massat about 95° C. This results in a molar ratio of barium to molybdenum of3:1. During the addition of the aqueous mixture, ammonia and carbondioxide are evolved. Thereafter, volatiles are removed from the reactionmass by heating to 150° C., while blowing with nitrogen. The residue isfiltered yielding 550 grams of an oil solution on the desiredmolybdenum-containing complex. Analysis of the product establishes thatabout 65% of the molybdenum employed in the reaction is retained in themolybdenum-containing complex thus produced.

EXAMPLE M-5

[0061] (A) A mixture of 44 parts (all parts refer to parts by weight) ofthe product of Example M-4(b), 10 parts mineral oil, and 24 parts of thereaction product of polyisobutene ({overscore (M)}n=750)-substitutedsuccinic anhydride with a commercial mixture of polyethylene polyamineshaving an average composition corresponding to that of tetraethylenepentamine (reacted in a ratio of equivalents of 1:1 according to theprocedure of U.S. Pat. No. 3,172,892, e.g., Example 12 thereof) isprepared and heated to about 75° C. over a 1.5 hour period. The weightratio of peptizing agent to overbased material is 5:95. To this solutionthere is added 520 parts of an aqueous ammonium molybdate solutionpreviously prepared by mixing 265 parts by weight of water and 265 partsby weight of a commercial ammonium molybdate (ammonium dimolybdate soldby the Climax Molybdenum Company having a composition corresponding tothe formula (NH₄)₂MO₂O₇ containing about 56.5% by weight molybdenum)over a 1.5 hour period while maintaining a temperature at about 70-80°C. resulting in a molar ratio of barium to molybdenum of 1:1.53. Theresulting reaction mass is heated under reflux conditions at about 150°C. for about 8.8 hours. Subsequently, the mixture is blown with nitrogenat about 5 parts per hour while maintaining the temperature at about150° C. for an additional 1.3 hours. The nitrogen blowing is thereafterceased, the mixture is maintained at about 150° C. for an additionalhour and the entire reaction mass is filtered. The filtrate contains thedesired molybdenum-containing complex and is characterized by having19.67% by weight molybdenum and 21.81% by weight barium.

[0062] (B) To a mixture of 2.285 grams of the overbased product ofExample M-4(b) and 125 grams of the peptizing agent referred to above(Example M-5(a)), there is added slowly over three hours 2600 grams ofan aqueous solution of ammonium paramolybdate tetrahydrate (prepared bymixing 1300 grams of the molybdate and 1300 grams of water) whilemaintaining a temperature slightly above 70° C. The weight ratio ofpeptizing agent to overbased product is 5:95 and the barium tomolybdenum molar ratio of 1:1.47. Ammonia, carbon dioxide, and water areevolved during the ensuing reaction. Thereafter, nitrogen is bubbledthrough the reaction mass to remove water and gases during which timethe product is heated to 170° C. for four hours. Then a commercialfilter aid is added and the mass is filtered. The filtrate weighs 2.710grams and contains 20.2% by weight molybdenum, 21.6% by weight barium,and 25.3% by weight oil.

[0063] Molybdenum Containing Thiocarbamates and Thiophosphates

[0064] As described above, the molybdenum composition may be amolybdenum containing thiocarbamate or thiophosphate. The molybdenumcompositions include molybdenum oxysulfide thiocarbamates and molybdenumoxysulfide thiophosphates. Thiocarbamates and their preparation aredescribed below. Molybdenum containing thiocarbamates, includingdithiocarbamates are known to those in the art. These materials aredescribed in U.S. Pat. Nos. 4,098,705, 4,259,194, 4,259,195, 4,265,773,4,272,387, 4,282,822, 4,283,295, 4,369,119, 4,395,423, and 4,402,840.These patents are incorporated by reference for their disclosure ofmolybdenum containing carbamates and methods of making the same.Examples of commercially available molybdenum containing thiocarbamatesinclude Sakura Lube 500 (20% molybdenum dithiocarbamate from SakuraChemical), and Molyvan 807 (5% molybdenum dithiocarbamate fromVanderbilt Chemical). The inventors have discovered that the molybdenumcontaining dithiocarbamates are useful in lubricating compositions whichrequire thermal stability. The level of molybdenum preferred formolybdenum containing dithiocarbamates is from about 200 to about 800,preferably from about 250 to about 600, more preferably from about 300to about 500 ppm.

[0065] In another embodiment, the molybdenum containing composition is amolybdenum thiophosphate. The molybdenum salts of thiophosphorus acidsare know those in the art. The thiophosphorus acids, includingdithiophosphoric acids, are described below. Molybdenum salts and themethods of their preparation are described in U.S. Pat. Nos. 3,223,625,3,256,184, 3,400,140, 3,494,866, 3,840,463, and 4,156,099. These patentsare hereby incorporated by reference for such disclosure.

[0066] Borated Overbased Salts

[0067] In one embodiment, the molybdenum containing compositions areused in combination with borated overbased metal salts. The boratedoverbased metal salts are prepared by reacting a boron compound with oneor more of the above overbased metal salts, or by using boric acid tooverbase an acidic organic compound. The borated overbased metal saltsare generally used in an amount from about 0.1% up to about 5%, or fromabout 0.5% up to about 3%, or from about 0.5% up to about 2% by weightof the lubricating compositions.

[0068] Boron compounds include boron oxide, boron oxide hydrate, borontrioxide, boron trifluoride, boron tribromide, boron trichloride, boronacid such as boric acid, tetraboric acid and metaboric acid, boronhydrides, boron amides and various esters of boron acids. The boronesters are preferably lower alkyl (1-7 carbon atoms) esters of boricacid. A preferred boron compound is boric acid. Generally, the overbasedsalts are reacted with a boron compound at about 50° C. to about 250°C., preferably from about 100° C. to about 200° C. The overbased saltsare generally reacted with a boron compound in amounts to provide atleast about 0.5%, or at least about 1% by weight boron to thecomposition. The overbased metal salt is generally reacted with a boroncompound in an amount to provide up to about 5%, 4, or up to about 4%,or up to about 3% by weight boron to the composition.

[0069] Borated overbased compositions, lubricating compositionscontaining the same and methods of preparing borated overbasedcompositions are found in U.S. Pat. No. 4,744,920, issued to Fischer etal; U.S. Pat. No. 4,792,410 issued to Schwind et al and PCT PublicationWO 88/03144. The disclosures relating to the above are herebyincorporated by reference.

[0070] In another embodiment, the borated overbased metal salts areprepared by reacting the acidic organic compound with a basic metalsalts in the presence of a boron compound. The metals include transitionmetals, such as zinc, copper, and cadmium. These borated overbasedcompositions and methods of their preparation are described in U.S. Pat.No. 5,064,545 (Steckel). This patent is incorporated by reference forsuch disclosure.

[0071] The following examples relate to borated overbased metal salts.

EXAMPLE B-1

[0072] (a) A mixture of 853 grams of methyl alcohol, 410 grams of blendoil, 54 grams of sodium hydroxide, and a neutralizing amount ofadditional sodium hydroxide is prepared. The amount of the latteraddition of sodium hydroxide is dependent upon the acid number of thesubsequently added sulfonic acid. The temperature of the mixture isadjusted to 49° C. A mixture (1070 grams) of straight chain dialkylbenzene sulfonic acid ({overscore (M)}w=430) and blend oil (42% byweight active content) is added while maintaining the temperature at49-57° C. Polyisobutenyl ({overscore (M)}n=950)-substituted succinicanhydride (145 grams) is added to the reaction vessel. Then, 838 gramsof sodium hydroxide (838 grams) are added and the temperature isadjusted to 71° C. The reaction mixture is blown with 460 grams ofcarbon dioxide. The mixture is flash stripped to 149° C., and filteredto clarity to provide the desired God product. The product is anoverbased sodium sulfonate having a base number (bromophenol blue) of440, a metal content of 19.4% by weight, a metal ratio of 20, a sulfateash content of 58% by weight, and a sulfur content of 1.3% by weight.

[0073] (b) A reaction vessel is charged with 1000 grams of the aboveoverbased sodium salt (Example B-1(a)), 0.13 gram of an antifoamingagent (kerosene solution of Dow Coring 200 Fluid having a viscosity of1000 cSt at 25° C.), and 133 grams of blend oil is heated to 74-79° C.with stirring. Then, 486 grams of boric acid are added to the reactionmixture. The reaction mixture is heated to 121° C. to liberate water ofreaction and 40-50% by weight of the CO₂ contained in the aboveoverbased sodium salt. The reaction mixture is heated to 154-160° C. andmaintained at that temperature until the free and total water content isreduced to 0.3% by weight or less and approximately 1-2% by weight,respectively. The reaction product is cooled to room temperature andfiltered.

EXAMPLE B-2

[0074] (a) A mixture of 1000 grams of a primarily branched chainmonoalkyl benzene sulfonic acid ({overscore (M)}w=500), 771 grams ofo-xylene, and 75.2 grams of polyisobutenyl ({overscore (M)}n=950)succinic anhydride is prepared and the temperature is adjusted to 46° C.Magnesium oxide (87.3 grams), acetic acid (35.8 grams), methyl alcohol(31.4 grams), and water (59 grams) are added sequentially to thereaction mixture. The reaction mixture is blown with 77.3 grains ofcarbon dioxide at a temperature of 49-54° C. Then, 87.3 grams ofmagnesium oxide, 31.4 grams of methyl alcohol and 59 grams of water areadded, and the reaction mixture is blown with 77.3 grams of carbondioxide at 49-54° C. The foregoing steps of magnesium oxide, methylalcohol and water addition, followed by carbon dioxide blowing arerepeated once. O-xylene, methyl alcohol and water are removed from thereaction mixture using atmospheric and vacuum flash stripping Thereaction mixture is cooled and filtered to clarity. The product is anoverbased magnesium sulfonate having a base number (bromophenol blue) of400, a metal content of 9.3% by weight. a metal ratio 14.7, a sulfateash content of 46.0%, and a sulfur content of 1.6% by weight.

[0075] (b) A reaction vessel is charged with 1000 grams of the aboveoverbased magnesium salt (Example B-2(a)) and 181 grams of diluent oilis heated to 79° C. Then, 300 grams of boric acid are added to thereaction mixture and the mixture is heated to 124° C. over a period of 8hours. The reaction mixture is maintained at 121-127° C. for 2-3 hoursuntil the magnesium content remains constant at 6.8% by weight. Anitrogen sparge is started and the reaction mixture is heated to 149° C.to remove water until the water content is 3% by weight or less. Thereaction mixture is filtered to provide the desired product.

[0076] The molybdenum containing composition may be used in combinationwith (i) an organic polysulfide or an ashless dithiocarbamatecomposition and (ii) a phosphorus or boron extreme pressure agent. Theorganic polysulfide or the ashless dithiocarbamate composition aregenerally used in an amount from about 0.5% up to about 5%, or fromabout 1% up to about 4%, or from about 2% up to about 3.57 by weight ofthe lubricating composition.

[0077] Organic Polysulfide or Ashless Dithiocarbamate ContainingComposition

[0078] The organic polysulfide is characterized as having sulfidelinkages having from at least 2 to about 10 sulfur atoms, preferably 2to about 6 sulfur atoms, more preferably 2 to about 4 sulfur atoms. Theorganic polysulfides are generally di-, tri- or tetrasulfidecompositions with trisulfide compositions preferred.

[0079] The organic polysulfides of the present invention provide fromabout 1% to about 3% sulfur to the lubricating compositions Generally,the organic polysulfides contain from about 10% to about 60% sulfur,preferably from about 20% to about 50%, and more preferably from about35% to about 45% sulfur. Materials which may be sulfurized to form theorganic polysulfides include oils, fatty acids or esters, or olefins, orpolyolefins. These materials are sulfurized by their reaction withsulfurizing agents, such as elemental sulfur, sulfur halides,combinations of sulfur with hydrogen sulfide, etc.

[0080] Oils which may be sulfurized are natural or synthetic oilsincluding mineral oils, lard oil, carboxylate esters derived fromaliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g.,myristyl oleate and oleyl oleate), sperm whale oil and synthetic spermwhale oil substitutes and synthetic unsaturated esters or glycerides.

[0081] Fatty acids generally contain from about 4 up to about 30, orfrom about 8 up to about 24 carbon atoms such as palmitoleic, oleic,ricinoleic, linoleic, oleostearic, etc. Sulfurized fatty acid esters areprepared from mixed unsaturated fatty acid esters such as those obtainedfrom animal fats and vegetable oils and including tall oil, linseed oil,rape oil, fish oil, sperm oil, etc.

[0082] The olefinic compounds which may be sulfurized contain at leastone olefinic double bond. The double bond is defined as a non-aromaticdouble bond; that is, one connecting two aliphatic carbon atoms. In itsbroadest sense, the olefin may he defined by the formula

R*¹R*²C═CR*³R*⁴

[0083] wherein each of R*¹, R*², R*³ and R*⁴ is hydrogen or an organicgroup. In general, the R groups in the above formula which are nothydrogen may be satisfied by such groups as —C(R*⁵)₃, —COOR*⁵,—CON(R*⁵)₂, —COON(R*⁵)₄, —COOM, —CN, —X, —YR*⁵ or —Ar, wherein: each R*⁵is independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl,substituted alkenyl or substituted aryl, with the proviso that any twoR*⁵ groups can be alkylene or substituted alkylene whereby a ring of upto about 12 carbon atoms is formed; M is one equivalent of a metalcation (preferably Group I or II, e.g., sodium, potassium, barium,calcium); X is halogen (e.g., chloro, bromo, or iodo); Y is oxygen ordivalent sulfur; Ar is an aryl or substituted aryl group of up to about12 carbon atoms. Any two of R*¹, R*², R*³ and R*⁴ may also together forman alkylene or substituted alkylene group; i.e., the olefinic compoundmay be alicyclic.

[0084] The olefinic compound is usually one in which each R* group whichis not hydrogen is independently alkyl, alkenyl or aryl group.Monoolefinic and diolefinic compounds, particularly the former, arepreferred, and especially terminal monoolefinic hydrocarbons; that is,those compounds in which R*³ and R*⁴ are hydrogen and R*¹ and R*² arealkyl or aryl, especially alkyl (that is, the olefin is aliphatic)having 1 to about 30, preferably 1 to about 16, more preferably 1 toabout 8, and more preferably 1 to about 4 carbon atoms. Olefiniccompounds having about 3 to about 30 and especially about 3 to about 16(most often less than about 9) carbon atoms are particularly desirable.

[0085] Isobutene, propylene and their dimers, trimers and tetramers, andmixtures thereof are especially preferred olefinic compounds. Of thesecompounds, isobutylene and diisobutylene are particularly desirablebecause of their availability and the particularly high sulfurcontaining compositions which can be prepared therefrom.

[0086] In one preferred embodiment, the organic polysulfide comprisesulfurized olefins, where the olefins are described above. For example,organic polysulfides may be prepared by the sulfochlorination of olefinscontaining four or more carbon atoms and further treatment withinorganic higher polysulfides according to U.S. Pat. No. 2.708,199.

[0087] In one embodiment, sulfurized olefins are produced by (1)reacting sulfur monochloride with a stoichiometric excess of a lowcarbon atom number olefin. (2) treating the resulting product with analkali metal sulfide in the presence of free sulfur in a mole ratio ofno less than 2:1 in an alcohol-water solvent, and (3) reacting thatproduct with an inorganic base. This procedure is described in U.S. Pat.No. 3,471,404, and the disclosure of U.S. Pat. No. 3,471,404 is herebyincorporated by reference for its discussion of this procedure forpreparing sulfurized olefins and the sulfurized olefins thus produced.Generally, the olefin reactant contains from about 2 to about 5 carbonatoms and examples include ethylene, propylene, butylene, isobutylene,amylene, etc.

[0088] The sulfurized olefins which are useful in the compositions ofthe present invention also may be prepared by the reaction, undersuperatmospheric pressure, of olefinic compounds with a mixture ofsulfur and hydrogen sulfide in the presence of a catalyst, followed byremoval of low boiling materials. This procedure for preparingsulfurized compositions which are useful in the present invention isdescribed in U.S. Pat. No. 4,191,659, the disclosure of which is herebyincorporated by reference for its description of the preparation ofuseful sulfurized compositions.

[0089] In one embodiment, the organic polysulfide may be prepared byreaction of a mercaptan and sulfur in the presence of a catalyst, suchas magnesium oxide, alumina catalyst. The mercaptans used to make thepolysulfide may be hydrocarbyl mercaptans, such as those represented bythe formula R—S—H, wherein R is a hydrocarbyl group as defined above. Inone embodiment, R is an alkyl, an alkenyl, cycloalkyl, or cyclo-alkenylgroup. R may also be a haloalkyl, hydroxyalkyl, or hydroxyalkylsubstituted (e.g. hydroxymethyl, hydroxyethyl, etc.) aliphatic groups. Rgenerally contains from about 2 to about 30 carbon atoms, or from about2 to about 24, or from about 3 to about 18 carbon atoms. Examplesinclude butyl mercaptan, amyl mercaptan, hexyl mercaptan, octylmercaptan, 6-hydroxymethyloctanethiol, nonyl mercaptan, decyl mercaptan,10-amino-dodecanethiol, dodecyl mercaptan,10-hydroxymethyl-tetradecanethiol, and tetradecyl mercaptan. Theseorganic polysulfides and processes for making them are disclosed in U.S.Pat. No. 4,564,709, issued to Koyama et al and U.S. Pat. No. 5,146,000,issued to Ozbalik. These patents are incorporated by reference for suchdisclose.

[0090] The following example relates to organic polysulfides.

EXAMPLE S-1

[0091] Sulfur (526 parts, 16.4 moles) is charged to a jacketed,high-pressure reactor which is fitted with an agitator and internalcooling coils. Refrigerated brine is circulated through the coils tocool the reactor prior to the introduction of the gaseous reactants.After sealing the reactor, evacuating to about 2 torr and cooling, 920parts (16.4 moles) of isobutene and 279 parts (8.2 moles) of hydrogensulfide are charged to the reactor. The reactor is heated using steam inthe external jacket, to a temperature of about 182° C. over about 1.5hours. A maximum pressure of 1350 psig is reached at about 168° C.during this heat-up. Prior to reaching the peak e reaction temperature,the pressure starts to decrease and continues to decrease steadily asthe gaseous reactants are consumed. After about 10 hours at a reactiontemperature of about 182° C., the pressure is 310-340 psig and the rateof pressure change is about 5-10 psig per hour. The unreacted hydrogensulfide and isobutene are vented to a recovery system. After thepressure in the reactor has decreased to atmospheric, the sulfurizedmixture is recovered as a liquid.

EXAMPLE S-2

[0092] Sulfur monochloride (2025 grains, 15.0 moles) is heated to 45° C.Through a sub-surface gas sparge, 1468 grams (26.2 moles) of isobutylenegas are fed into the reactor over a 5-hour period. The temperature ismaintained between 45-50° C. At the end of the sparging, the reactionmixture increases in weight of 1352 grams. In a separate reaction vesselare added 2150 grams (16.5 moles) of 60% flake sodium sulfide, 240 grams(7.5 moles) sulfur, and a solution of 420 ml. of isopropanol in 4000 ml.of water. The contents are heated to 40° C. The adduct of the sulfurmonochloride and isobutylene previously prepared is added over athree-quarter hour period while permitting the temperature to rise to75° C. The reaction mixture is heated to reflux for 6 hours, andafterward the mixture is permitted to form into separate layers. Thelower aqueous layer is discarded. The upper organic layer is mixed withtwo liters of 10% aqueous sodium hydroxide, and the mixture is heated toreflux for 6 hours. The organic layer is again removed and washed withone liter of water. The washed product is dried by heating at 90° C. and30 mm. Hg, pressure for 30 minutes. The residue is filtered throughdiatomaceous earth filter aid to give 2070 grams of a clearyellow-orange liquid

[0093] The ashless dithiocarbamate compositions include reactionproducts of a dithiocarbamic acid or salt and an unsaturated amide,carboxylic acid, anhydride, or ester, or ether, alkylene-coupleddithiocarbamate, and bis(S-alkyldithiocarbamoyl) disulfides. Thedithiocarbamate compounds (A) may be prepared by reacting adithiocarbamic acid or salt with an unsaturated compound. Thedithiocarbamate compositions may also be prepared by simultaneouslyreacting an amine, carbon disulfide and an unsaturated compound.Generally, the reaction occurs at a temperature from about 25° C. toabout 125° C., or from about 50° C. to about 100° C. U.S. Pat. Nos.4,758,362 and 4,997,969 describe dithiocarbamate compositions andmethods of making the same. These patents are hereby incorporated byreference for their disclosure of dithiocarbamate compositions andmethod of making the same.

[0094] The dithiocarbamic acid or salt used to prepare thedithiocarbamate compositions are prepared by reacting an amine withcarbon disulfide. The amine may be a primary or a secondary amine. Theamines may be primary or secondary amines, with secondary amines mostpreferred. The amines generally may contain hydrocarbyl groups. Eachhydrocarbyl group may independently contain from one up to about 40, orfrom about two up to about 30, or from three up to about 24, or even upto about 12 carbon atoms. Examples of groups which may be on the aminesinclude ethyl, propyl, butyl, hexyl, octyl and dodecyl groups.

[0095] In one embodiment, the amines are primary amines. Examples ofprimary amines useful in the present invention include ethylamine,propylamine, butylamine, 2-ethylhexylamine, octylamine, anddodecylamine.

[0096] In one embodiment, the primary amine is a fatty (C₈₋₃₀) aminewhich include n-octylamine, n-decylamine, n-dodecylamine,n-tetradecylamine, n-hexadecylamine, n-octadecylamine, oleyamine, etc.Also useful fatty amines include commercially available fatty aminessuch as “Armeen” amines (products available from Akzo Chemicals,Chicago, Ill.), such as Akzo's Ameen C, Armeen O. Armeen OL, Armeen T,Armeen HT, Armeen S and Armeen SD, wherein the letter designationrelates to the fatty group, such as cocoa, oleyl, tallow, or stearylgroups.

[0097] Other useful primary amines include primary ether amines, such asthose represented by the formula, R″(OR′)_(x)NH₂, wherein R′ is adivalent alkylene group having from about 2 to about 6 carbon atoms; xis a number from one to about 150, or from one to about five, or one;and R″ is a hydrocarbyl group of about 5 to about 150 carbon atoms. Anexample of an ether amine is available under the name SURFAM® aminesproduced and marketed by Mars Chemical Company, Atlanta, Ga. Preferredetheramines are exemplified by those identified as SURFAM P14B(decyloxypropylamine), SURFAM P16A (linear C₁₆), SURFAM P17B(tridecyloxypropylamine). The carbon chain lengths (i.e., C₁₄, etc.) ofthe SURFAMS described above and used hereinafter are approximate andinclude the oxygen ether linkage.

[0098] In one embodiment, the amine is a tertiary-aliphatic primaryamine. Generally, the aliphatic group, preferably an alkyl group,contains from about 4 to 44, about 30, or from about 6 to about 24, orfrom about 8 to about 22 carbon atoms. Usually the tertiary alkylprimary amines are monoamines represented by the formula R₁-C(R₁′)₂-NH₂,wherein R₁ is a hydrocarbyl group containing from one to about 27 carbonatoms and R₁′ is a hydrocarbyl group containing from 1 to about 12carbon m atoms. Such amines are illustrated by tert-butylamine,tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine,tert-decylamine, tert-dodecylamine, tert-tetradecylamine,tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, andtert-octacosanylamine.

[0099] Mixtures of amines are also useful for the purposes of thisinvention. Illustrative of amine mixtures of this type are “Primene 81R”which is a mixture of C₁₁-C₁₄ tertiary alkyl primary amines and “PrimeneJMT” which is a similar mixture of C₁₈-C₂₂, tertiary alkyl primaryamines (both are available from Rohm and Haas Company). The tertiaryalkyl primary amines and methods for their preparation are known tothose of ordinary skill in the art. The tertiary alkyl primary amineuseful for the purposes of this invention and methods for theirpreparation are described in U.S. Pat. No. 2,945,749 which is herebyincorporated by reference for its teaching in this regard.

[0100] In another embodiment, the amine is a secondary amine. Specificof secondary amines include dimethylamine, diethylamine, dipropylamine,dibutylamine, diamylamine, dihexylamine, diheptylamine,methylethylamine, ethylbutylamine, ethylamylamine and the like. In oneembodiment, the secondary amines may be cyclic amines such aspiperidine, piperazine, morpholine, etc.

[0101] In one embodiment, the dithiocarbamate compound (A) is preparedby reacting one or more dithiocarbamic acids or salts with anunsaturated amide. Examples of unsaturated amides include acrylamide,N,N′-methylene bis(acrylamide), methacrylamide, crotonamide, and thelike. In one embodiment, the dithiocarbamate containing composition isderived from the reaction product of a diamylamine or dibutylamine withcarbon disulfide which forms a dithiocarbamic acid or a salt which isultimately reacted with a acrylamide. If the reaction products of thedithiocarbamic is, acid or salt and an unsaturated amide has additionalNH group which are capable of reacting, then the reaction product may befurther reacted with a linking or a coupling compound, such asformaldehyde or paraformaldehyde. The reaction products ofdithiocarbamic acids and salts with unsaturated amides are disclosed inU.S. Pat. Nos. 4,758,362 (Butke) and 4,997,969 (Luciani) which areincorporated by reference for their disclosures of dithiocarbamic acidsand salts, unsaturated amides and their reaction products includingcoupled products.

[0102] In one embodiment, ashless the dithiocarbamate composition (A) isa reaction product of a dithiocarbamic acid or salt with an unsaturatedacid, anhydride or ester. Examples of unsaturated carboxylic acids andanhydrides include acrylic acid, methacrylic acid, itaconic acid, maleicacid, fumaric acid, and maleic anhydride. If an unsaturated carboxylicacid or anhydride is used, an ester may then be formed by subsequentreaction of the dithiocarbamate-unsaturated carboxylic acid or anhydrideadduct with an alcohol such as those alcohols discussed herein. In oneembodiment, the alcohol has from 1 to about 12 carbon atoms.

[0103] In one embodiment, the unsaturated carboxylic acid, or anhydrideor ester X includes maleic, fumaric, acrylic, methacrylic, itaconic,citraconic acids and esters. The ester may be represented by one of theformulae: (R₁)₂C═C(R₁)C(O)OR₂, or R₂O—(O)C—HC═CH—C(O)OR₂, wherein eachR₁ and R₂ are independently hydrogen or a hydrocarbyl group having 1 toabout 18, or to about 12, or to about 8 carbon atoms, R₁ is hydrogen oran alkyl group having from 1 to about 6 carbon atoms. In one embodiment,R₁ is preferably hydrogen or a methyl group.

[0104] Examples of unsaturated carboxylic esters include methylacrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethylacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, ethyl maleate,butyl maleate and 2-ethylhexyl maleate. The above list includes mono- aswell as diesters of maleic, fumaric, and itaconic acids and anhydrides.In one embodiment, the dithiocarbamate acid or salt is formed fromdiethylamine or dibutylamine and carbon disulfide. The resultingdithiocarbamic acid is then reacted with methyl acrylate.

[0105] In another embodiment, the unsaturated carboxylic ester is avinyl ester. The vinyl ester may he represented by the formulaR₁CH═CH—O(O)CR₂, wherein R₁ is a hydrocarbyl group having from 1 toabout 30, or to about 12 carbon atoms, preferably hydrogen, and R₂ is ahydrocarbyl group having 1 to about 30, or to about 12, or to about 8carbon atoms. Examples of vinyl esters include vinyl acetate, vinyl2-ethylhexanoate, vinyl butanoate, etc.

[0106] In one embodiment, the dithiocarbamate compound (A) is a reactionproduct of a dithiocarbamic acid or salt and a vinyl ether. The vinylether is represented by the formula R₁—CH═CH—OR₂ wherein R₁ isindependently hydrogen or a hydrocarbyl group having from 1 up to about30, or up to about 24, or up to about 12 carbon atoms. R₁ is ahydrocarbyl group defined the same as R₁. Examples of vinyl ethersinclude methyl vinyl ether, propyl vinyl ether, 2-ethylhexyl vinyl etherand the like.

[0107] In one embodiment, the dithiocarbamate compound (A) is analkylene-coupled dithiocarbamate. The alkylene-coupled dithiocarbamatesuseful in the present invention may be prepared by the reaction of asalt of a dithiocarbamic acid, described above, with a suitabledihalogen containing hydrocarbon. The reaction is generally carried outat a temperature within the range from about 25° C. up to about 150° C.,or up to about 100° C. U.S. Pat. No. 3,876,550 issued to Holubecdescribes alkylene dithiocarbamate compounds, and U.S. Pat. Nos.1,726,647 and 1,736,429, issued to Cadwell describe, phenylmethylenebis(dithiocarbamates) and methods of making the same. These patents areincorporated by reference for their teachings related to dithiocarbamatecompounds and methods for preparing the same. In one embodiment, thealkylene-coupled dithiocarbamate is derived from di-n-butyl amine,carbon disulfide and methylene dichloride.

[0108] In another embodiment, the dithiocarbamate compound is abis(S-alkyldithiocarbamoyl) disulfide. These materials have previouslybeen referred to as sulfur-coupled dithiocarbamates. The disulfides areprepared by (A) reacting a sulfur halide with about a stoichiometricequivalent of (i) at least one olefinic hydrocarbon, or (ii) an aldehydeor ketone, at a temperature and for a period of time sufficient toproduce a di(halohydrocarbyl)sulfur intermediate or a dialdehyde ordiketo sulfur intermediate, and (B) reacting the intermediate with asalt of a dithiocarbamate in an amount sufficient generally to replaceboth halo groups with the dithiocarbamate groups or to react with bothcarbonyl groups of the dialdehyde or diketone. The sulfur halideutilized in the first step (A) may be sulfur monochloride (i.e., S₂Cl₂),sulfur dichloride, sulfur monobromide, sulfur dibromide, or mixtures ofany of the above sulfur halides with elemental sulfur in varyingamounts.

[0109] The sulfur halide utilized in the first step (A) may be sulfurmonochloride (i.e., S₂Cl₂), sulfur dichloride, sulfur monobromide,sulfur dibromide, or mixtures of any of the above sulfur halides withelemental sulfur in varying amounts. Various olefins and olefin mixturesmay be used as the starting material in step (A). The olefins aredisclosed below for the organic polysulfide. Specific examples ofaldehydes that may be reacted with sulfur halides include, for example,acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde,2-ethyl-hexanal, and cyclohexanecarboxaldehyde. Examples of ketonesinclude dimethyl ketone, methyl ethyl ketone, diethyl ketone, methylisopropyl ketone, methyl isobutyl ketone, etc.

[0110] The reaction between the sulfur intermediate and thedithiocarbamate salts generally is conducted from ambient temperature tothe reflux temperature of the mixture. The reaction is conducted untilthe reaction is completed which is generally from about 5 to about 24hours. At the end of the reaction, the aqueous phase is separated, andthe product is recovered from the organic phase.

[0111] The bis(S-alkyldithiocarbamoyl) disulfides also may be preparedby a process which comprises the steps of (A) reacting an olefinichydrocarbon with a halogen to produce a halogen-containing intermediate,and (B) reacting said intermediate with an alkali metal sulfide and asalt of a dithiocarbamate in an amount sufficient to replace the halogengroups present partially with dithiocarbamate groups and/or partiallywith sulfide groups. The bis(S-alkyldithiocarbamoyl) disulfides aredescribed in U.S. Pat. No. 2,599,350, issued to Rudel et al. This patentis incorporated by reference for its disclosure ofbis(S-alkyldithiocarbamoyl) disulfide.

[0112] Phosphorus or Boron Agents:

[0113] As described above, the molybdenum containing composition saltsare used in combination with (i) an organic polysulfide or an ashlessdithiocarbamate containing composition, and (ii) at least one phosphorusor boron containing antiwear/extreme pressure agent selected from thegroup consisting of a metal thiophosphate, a phosphoric acid ester orsalt thereof, a phosphorus-containing carboxylic acid, ester, ether, oramide, a borated dispersant, an alkali metal borate, a borated fattyamine, a borated phospholipid, and a borate ester. The phosphorus orboron containing agents are typically present in the lubricants andfunctional fluids at a level of up to about 20% by weight, preferably upto about 10% by weight, based on the total weight of the lubricant,functional fluid, or grease. Typically, the phosphorus or boroncontaining antiwear/extreme pressure agent is present at a level fromabout 0.1%, or from about 0.5%, or from about 0.8% by weight. Thephosphorus or boron containing antiwear/extreme pressure agent ispresent in an amount up to about 10%, or up to about 3%, or up to about2% by weight. In one embodiment, the lubricating compositions,functional fluids, and greases contain more than 0.01% phosphorus,preferably greater than 0.05% phosphorus.

[0114] Examples of phosphorus or boron containing antiwear/extremepressure agents include a metal thiophosphate; a phosphoric acid esteror salt thereof; a phosphorus-containing carboxylic acid, ester, ether,or amide; a borated dispersant; an alkali metal borate; a borated fattyamine; a borated phospholipid, and a borate ester. The phosphorus acidsinclude the phosphoric, phosphonic, phosphinic and thiophosphoric acidsincluding dithiophosphoric acid as well as the monothiophosphoric acid,thiophosphinic and thiophosphonic acids.

[0115] In one embodiment, phosphorus or boron containingantiwear/extreme pressure agent is a phosphorus acid ester prepared byreacting one or more phosphorus acid or anhydride with an alcoholcontaining from one, or about 3 carbon atoms. The alcohol generallycontains up to about 30, or up to about 24, or up to about 12 carbonatoms. The phosphorus acid or anhydride is generally an inorganicphosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide,phosphorus tetroxide, phosphorus acid, phosphorus halide, lowerphosphorus esters, or a phosphorus sulfide, including phosphoruspentasulfide, and the like. Preferred phosphorus acids or anhydrides arephosphorus pentoxide, phosphorus pentasulfide and phosphorustrichloride. Lower phosphorus acid esters generally contain from 1 toabout 7 carbon atoms in each ester group. The phosphorus acid ester maybe a mono-, di- or triphosphoric acid ester. Alcohols used to preparethe phosphorus acid esters include butyl, amyl, 2-ethylhexyl, hexyl,octyl, oleyl, and cresol alcohols. Examples of commercially availablealcohols include Alfol 810 (a mixture of primarily straight chain,primary alcohols having from 8 to 10 carbon atoms); Alfol 1218 (amixture of synthetic, primary, straight-chain alcohols containing 12 to18 carbon atoms); Alfol 20+alcohols (mixtures of C₁₈-C₂₈, primaryalcohols having mostly C₂, alcohols as determined by CLC(gas-liquid-chromatography)); and Alfol 22+alcohols (C₁₈-C₂₈ primaryalcohols containing primarily C₂, alcohols). Alfol alcohols areavailable from Continental Oil Company.

[0116] Another example of a commercially available alcohol mixtures areAdol 60 (about 75% by weight of a straight chain C₂₂ primary alcohol,about 15% of a C₂₀ primary alcohol and about 8% of C₁₈ and C₂₄ alcohols)and Adol 320 (oleyl alcohol). The Adol alcohols are marketed by AshlandChemical.

[0117] A variety of mixtures of monohydric fatty alcohols derived fromnaturally occurring triglycerides and ranging in chain length of fromabout C₈ to C₁₈ are available from Procter & Gamble Company. Thesemixtures contain various amounts of fatty alcohols containing mainly 12,14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty alcoholmixture containing 0.5% of C₁₀ alcohol, 66.0% of C₁₂ alcohol, 26.0% ofC₁₄ alcohol and 6.5% of C₁₆ alcohol.

[0118] Another group of commercially available mixtures include the“Neodol” products available from Shell Chemical Co. For example, Neodol23 is a mixture of C₁₂ and C₁₃ alcohols; Neodol 25 is a mixture of C₁₂and C₁₅ alcohols; and Neodol 45 is a mixture of C₁₄ to C₁₅ linearalcohols. Neodol 91 is a mixture of C₉, C₁₀ and C₁₁ alcohols.

[0119] Fatty vicinal diols also are useful and these include thoseavailable from Ashland Oil under the general trade designation Ado 114and Adol 158. The former is derived from a straight chain alpha olefinfraction of C₁₁-C₁₄, and the latter is derived from a C₁₅-C₁₈ fraction.

[0120] Examples of useful phosphorus acid esters include the phosphoricacid esters prepared by reacting a phosphoric acid or anhydride withcresol alcohols. An example of these phosphorus acid esters istricresylphosphate.

[0121] In another embodiment, the phosphorus or boron antiwear/extremepressure agent is a thiophosphorus acid ester or salt thereof. Thethiophosphorus acid ester may be prepared by reacting a phosphorussulfide, such as those described above. with an alcohol, such as thosedescribed above. The thiophosphorus acid esters may be mono- ordithiophosphorus acid esters. Thiophosphorus acid esters are alsoreferred to generally as thiophosphoric acids.

[0122] In one embodiment, the phosphorus acid ester is amonothiophosphoric acid ester or a monothiophosphate. Monothiophosphatesmay be prepared by the reaction of a sulfur source with a dihydrocarbylphosphite. The sulfur source may for instance be elemental sulfur. Thesulfur source may also be a monosulfide, such as a sulfur coupledoletfin or a sulfur coupled dithiophosphate. Elemental sulfur is apreferred sulfur source. The preparation of monothiophosphates isdisclosed in U.S. Pat. No. 4,755,311 and PCT Publication WO 87/07638,which are incorporated herein by reference for their disclosure ofmonothiophosphates, sulfur sources, and the process for makingmonothiophosphates. Monothiophosphates may also be formed in thelubricant blend by adding a dihydrocarbyl phosphite to a lubricatingcomposition containing a sulfur source, such as a sulfurized olefin. Thephosphite may react with the sulfur source under blending conditions(i.e., temperatures from about 30° C. to about 100° C. or higher) toform the monothiophosphate.

[0123] In another embodiment, the phosphorus or boron antiwear/extremepressure agent is a dithiophosphoric acid or phosphorodithioic acid. Thedithiophosphoric acid may be represented by the formula (RO)₂PSSHwherein each R is independently a hydrocarbyl group containing fromabout 3 to about 30 carbon atoms. R generally contains up to about 18,or to about 12, or to about 8 carbon atoms. Examples R includeisopropyl, isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl,methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl,decyl, dodecyl, and tridecyl groups. Illustrative lower alkylphenyl Rgroups include butylphenyl, amylphenyl, heptylphenyl, etc. Examples ofmixtures of R groups include: 1-butyl and 1-octyl: 1-pentyl and2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isoamyl; 2-propyland 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl andisooctyl.

[0124] In one embodiment, the dithiophosphoric acid may be reacted withan epoxide or a glycol. This reaction product may be used alone, orfurther reacted with a phosphorus acid, anhydride, or lower ester. Theepoxide is generally an aliphatic epoxide or a styrene oxide. Examplesof useful epoxides include ethylene oxide, propylene oxide, buteneoxide, octene oxide, dodecene oxide, styrene oxide, etc Propylene oxideis preferred. The glycols may be aliphatic glycols having from 1 toabout 12, preferably about 2 to about 6, more preferably 2 or 3 carbonatoms, or aromatic glycols. Glycols include ethylene glycol, propyleneglycol, catechol, resorcinol, and the like. The dithiophosphoric acids,glycols, epoxides, inorganic phosphorus reagents and methods of reactingthe same are described in U.S. Pat. No. 3,197,405 and U.S. patent3,544,465 which are incorporated herein by reference for theirdisclosure to these.

[0125] The following Examples P-1 and P-2 exemplify the preparation ofuseful phosphorus acid esters.

EXAMPLE P-1

[0126] Phosphorus pentoxide (64 grams) is added at 58° C. over a periodof 45 minutes to 514 grams of hydroxypropylO,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reactingdi(4-methyl-2-pentyl)-phosphorodithioic acid with 1.3 moles of propyleneoxide at 25° C.). The mixture is heated at 75° C. for 2.5 hours, mixedwith a diatomaceous earth and filtered at 70° C. The filtrate contains11.8% by weight phosphorus, 15.2% by weight sulfur, and an acid numberof 87 (bromophenol blue).

EXAMPLE P-2

[0127] A mixture of 667 grams of phosphorus pentoxide and the reactionproduct of 3514 grams of diisopropyl phosphorodithioic acid with 986grams of propylene oxide at 50° C. is heated at 85° C. for 3 hours andfiltered. The filtrate contains 15.3% by weight phosphorus, 19.6% byweight sulfur, and an acid number of 126 (bromophenol blue).

[0128] Acidic phosphoric acid esters may be reacted with an aminecompound or a metallic base to form an amine or metal salt. The saltsmay be formed separately and then the salt of the phosphorus acid estermay be added to the lubricating composition. Alternately, the salts mayalso be formed in situ when the acidic phosphorus acid ester is blendedwith other components to form a fully formulated lubricatingcomposition.

[0129] The amine salts of the phosphorus acid esters may be formed fromammonia, or an amine, including monoamines and polyamines. The aminesmay be primary amines, secondary amines or tertiary amines. In oneembodiment, the amines are one or more of the amines described above forpreparing the dithiocarbamates. Useful amines include those aminesdisclosed in U.S. Pat. No. 4,234,435 at Col. 21, line 4 to Col. 27, line50, these passages being incorporated herein by reference

[0130] The monoamines generally contain from 1 up to about 24 carbonatoms, or up to about 12, or up to about 6 carbon atoms. Examples ofmonoamines include methylamine, ethylamine, propylamine, butylamine,octylamine, and dodecylamine, dimethylamine, diethylamine,dipropylamine, dibutylamine, methyl butylamine, ethyl hexylamine,trimethylamine, tributylamine, methyl diethylamine, ethyl dibutylamine,etc.

[0131] In one embodiment, the amine may be a fatty (C₄ ₃₀) amine whichinclude n-hexylamine, n-octylamine, n-decylaminie, n-dodecylamine,n-tetradecylamine, n-hexadecylamine, n-octadecylamine, oleylamine, etc.Also useful fatty amines include commercially available fatty aminessuch as “Armeen” amines (products available from Armak Chemicals,Chicago, Ill.), such as Armak's Armeen-C, Armeen-O, Armeen-OL, Armeen-T,Armeen-HT, Armeen S and Armeen SD, wherein the letter designationrelates to the fatty group, such as cocoa, oleyl, tallow, or soyagroups.

[0132] Other useful amines include primary ether amines, such as thoserepresented by the formula, R″(OR′)_(x)NH₂, wherein R′ is a divalentalkylene group having about 2 to about 6 carbon atoms, x is a numberfrom one to about 150 (preferably one), and R″ is a hydrocarbyl group ofabout 5 to about 150 carbon atoms. An example of an ether amine isavailable under the name SURFAM® amines produced and marketed by MarsChemical Company, Atlanta, Ga. Preferred etheramines are exemplified bythose identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A(linear C₁₆), SURFAM P17B (tridecyloxypropylamine). The carbon chainlengths (i.e., C₁₄, etc.) of the SURFAMS described above and usedhereinafter are approximate and include the oxygen ether linkage.

[0133] In one embodiment, the amine may be a hydroxyamine. Typically,the hydroxyamines are primary, secondary or tertiary alkanol amines ormixtures thereof. Such amines can be represented by the formulae:H₂—N—R′—OH, H(R′₁)N—R′—OH, and (R′₁)₂—N—R′—OH, wherein each R′₁ isindependently a hydrocarbyl group having from one to about eight carbonatoms or hydroxyhydrocarbyl group having from one to about eight carbonatoms, or from one to about four, and R′ is a divalent hydrocarbyl groupof about two to about 18 carbon atoms, or from two to about four. Thegroup —R′—OH in such formulae represents the hydroxyhydrocarbyl group.R′ can be an acyclic, alicyclic or aromatic group. Typically, R′ is anacyclic straight or branched alkylene group such as an ethylene,propylene, 1,2-butylene, 1,2-octadecylene, etc. group. Where two R′1groups are present in the same molecule they can be joined by a directcarbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen orsulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples ofsuch heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and thelike. Typically, however, each R′1 is independently a methyl, ethyl,propyl, butyl, pentyl or hexyl group Examples of these alkanolaminiesinclude mono-, di-, and triethanolamine, diethylethanolamine,ethylethanolamiine, butyldiethanolamine, etc.

[0134] The hydroxyamines may also be an etherN-(hydroxyhydrocarbyl)amine These are hydroxypoly(hydrocarbyloxy)analogs of the above-described hydroxyamines (these analogs also includehydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyhydrocarbyl)amines can he conveniently prepared by reaction of one or more of theabove epoxides with aforedescribed amines and may he represented by theformulae: H₂N—(R′O)_(x)H, H(R′₁)—N—(R′O)_(x)—H, and(R′₁)₂—N—(R′O)_(x)—H, wherein x is a number from about 2 to about 15 andR, and R′ are as described above. R′₁ may also be ahydroxypoly(hydrocarbyloxy) group.

[0135] The amines may be hydroxyamines, such as those represented by theformula

[0136] wherein R₁ is a hydrocarbyl group generally containing from about6 to about 30 carbon atoms; R₂ and each R₃ is independently an alkylenegroup containing up to about 5 carbon atoms, preferably an ethylene orpropylene group; a is zero or one; and each z is independently a numberfrom zero to about 10, with the proviso that at least one z is at leastone. These hydroxyamines can be prepared by techniques well known in theart and many such hydroxyamines are commercially available. The hydroxyamines include mixtures of amines such as obtained by the hydrolysis offatty oils (e.g., tallow oils, sperm oils, coconut oils, etc.). Specificexamples of fatty amines, containing from about 6 to about 30 carbonatoms, include saturated as well as unsaturated aliphatic amines, suchas octyl amine, decyl amine, lauryl amine, stearyl amine, oleyl amine,dodecyl amine, and octadecyl amine.

[0137] Useful hydroxyamines wherein a in the above formula is zeroinclude 2-hydroxyethyl, hexylamine; 2-hydroxyethyloctylamine;2-hydroxyethyl, pentadecyl-amine; 2-hydroxyethyl, oleylamine;2-hydroxyethyl,soyamine; bis(2-hydroxyethyl) hexylamine;bis(2-hydroxyethyl)oleylamine; and mixtures thereof. Also included arethe comparable members wherein in the above formula at least one of z isat least 2, as for example, 2-hydroxyethoxyethyl, hexylamine.

[0138] A number of hydroxyamines wherein a in the above formula is zeroare available from the Armak Chemical Division of Akzona, Inc., Chicago,Ill. under the general trade designations “Ethomeen” and “Propomeen”.Specific examples of such products include: Ethomeen C/15 which is anethylene oxide condensate of a coco alkyl amine containing about 5 molesof ethylene oxide; Ethomeen C/20 and C/25 which are ethylene oxidecondensation products from coco alkyl amine containing about 10 and 15moles of ethylene oxide, respectively; Ethomeen O/12 which is anethylene oxide condensation product of oleylamine containing about 2moles of ethylene oxide per mole of amine; Ethomeen S/15 and S/20 whichare ethylene oxide condensation products with stearyl amine containingabout 5 and 10 moles of ethylene oxide per mole of amine, respectively;Ethomeen T/12, T/15 and T/25 which are ethylene oxide condensationproducts of tallow amine containing about 2, 5 and 15 moles of ethyleneoxide per mole of amine, respectively; and Propomeen O/12 which is thecondensation product of one mole of oleylamine with 2 moles propyleneoxide.

[0139] Commercially available examples of alkoxylated amines where a inthe above formula is one include Ethoduomeen T/13 and T/20 which areethylene oxide condensation products of N-tallow trimethylenediaminecontaining 3 and 10 moles of ethylene oxide per mole of diamine,respectively.

[0140] The amine may also be a polyamine. The polyamines includealkoxylated diamines, fatty diamines, alkylenepolyamines, hydroxycontaining polyamines, condensed polyamines and heterocyclic polyamines.Commercially available examples of alkoxylated diamines include thoseamines where a in the above formula is one. Examples of these aminesinclude Ethoduomeen T/13 and T/20 which are ethylene oxide condensationproducts of N-tallowtrimethylenediaminie containing 3 and 10 moles ofethylene oxide per mole of diamine, respectively.

[0141] In another embodiment, the polyamine is a fatty diamine. Thefatty diamines include mono- or dialkyl, symmetrical or asymmetricalethylenediamines. propanediamines (1,2, or 1,3), and polyamine analogsof the above Suitable commercial fatty polyamines are Duomeen C(N-coco-1,3-diaminopropane), Duomeen S (N-soya-1,3-diaminopropane),Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O(N-oleyl-1,3-diaminopropane) “Duonieens” are commercially available fromArmak Chemical Co., Chicago, Ill.

[0142] In another embodiment, the amine is an alkylenepolyamine.Alkylenepolyamines are represented by the formulaHR₁N-(Alkylene-N)_(n)-(R₁)₂, herein each R₁ is independently hydrogen,or an aliphatic or hydroxy-substituted aliphatic group of up to about 30carbon atoms; {overscore (M)}n is a number from 1 to about 10, or fromabout 2 to about 7, or from about 2 to about 5; and the “Alkylene” grouphas from 1 to about 10 carbon atoms, or from about 2 to about 6, or fromabout 2 to about 4. In another embodiment, R₁ is defined the same as R′₁above. Such alkylenepolyamines include methylenepolyamines,ethylenepolyamines. butylenepolyamines, propylenepolyamines,pentylenepolyamines, etc. The higher homologs and related heterocyclicamines, such as piperazines and N-amino alkyl-substituted piperazines,are also included. Specific examples of such polyamines areethylenediamine, triethylenetetramine, tris-(2-aminoethyl)amine.propylenediamine, trimethylenediamine, tripropylenetetramine,triethylenetetraamine, tetraethylenepentamine, hexaethyleneheptamine,pentaethylenehexamine, etc. Higher homologs obtained by condensing twoor more of the above-noted alkyleneamines are similarly useful as aremixtures of two or more of the aforedescribed polyamines.

[0143] In one embodiment, the polyamine is an ethylenepolyamine. Suchpolyamines are described in detail under the heading Ethylene Amines inKirk Othmer's “Encyclopedia of Chemical Technology”, 2d Edition, Vol. 7,pages 22-37, Interscience Publishers, New York (1965).Ethylenepolyamines are often a complex mixture of polyalkylenepolyaminesincluding cyclic condensation products. Other useful types of polyaminemixtures are those resulting from stripping of the above-describedpolyamine mixtures to leave, as residue, what is often termed “polyaminebottoms”. In general, alkylenepolyamine bottoms can be characterized ashaving less than 2%, usually less than 1% (by weight) material boilingbelow about 200° C. A typical sample of such ethylenepolyamine bottomsobtained from the Dow Chemical Company of Freeport, Tex. designated“E-100” has a specific gravity at 15.6° C. of 1.0168, a percent nitrogenby weight of 33.15 and a viscosity at 40° C. of 121 cetitistokes. Gaschromatography analysis of such a sample contains about 0.93% “LightEnds” (most probably diethylenetriamine), 0.72% tirethylenetetraamine,21.74% tetraethylenepentaamine and 76.61% pentaethylenehexamine andhigher analogs These alkylenepolyamine bottoms include cycliccondensation products, such as piperazine, and higher analogs ofdiethylenetriamine, triethylenetetramine and the like. Thesealkylenepolyamine bottoms may be reacted solely with the acylating agentor they may be used with other amines, polyamines, or mixtures thereof.

[0144] Another useful polyamine is a condensation reaction between atleast one hydroxy compound with at least one polyamine reactantcontaining at least one primary or secondary amino group. The hydroxycompounds are preferably polyhydric alcohols or polyhydric amines. Thepolyhydric alcohols are described below. In one embodiment, the hydroxycompounds are polyhydric amines. Polyhydric amines include any of theabove-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having from twoto about 20, or from two to about four carbon atoms. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine,tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis (2-hydroxypropyl) ethylenediamine, andN,N,N′,N′-tetrakis (2-hydroxyethyl) ethylenediamine, preferablytris(hydroxymethyl) aminomethane (THAM).

[0145] Polyamines which may react with the polyhydric alcohol or amineto form the condensation products or condensed amines, are describedabove. Preferred polyamines include triethylenetetramine (TETA),tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines such as the above-described “amine bottoms”. Thecondensation reaction of the polyamine reactant with the hydroxycompound is conducted at an elevated temperature, usually from about 60°C. to about 265° C., or from about 220° C. to about 250° C. in thepresence of an acid catalyst.

[0146] The amine condensates and methods of making the same aredescribed in PCT publication WO 86/05501 and U.S. Pat. No. 5,230,714(Steckel) which are incorporated by reference for its disclosure to thecondensates and methods of making. A particularly useful aminecondensate is prepared from HPA Taft Amines (amine bottoms availablecommercially from Union Carbide Co. with typically 34.1% by weightnitrogen and a nitrogen distribution of 12.3% by weight primary amine,14.4% by weight secondary amine and 7.4% by weight tertiary amine), andtris(hydroxymethyl)aminomethane (THAM).

[0147] In another embodiment, the polyamines are polyoxyalkylenepolyamines, e.g. polyoxyalkylene diamines and polyoxyalkylenietriamines, having average molecular weights ranging from about 200 toabout 4000, or from about 400 to about 2000. The preferredpolyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name “Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.”.U.S. Pat. Nos. 3,804,763 and 3,948,800 are expressly incorporated hereinby reference for their disclosure of such polyoxyalkylene polyamines andacylated products made therefrom.

[0148] In another embodiment, the polyamines are hydroxy-containingpolyamines. Hydroxy-containing polyamine analogs of hydroxy monoamines,particularly alkoxylated alkylenepolyamines, e.g.,N,N(diethanol)ethylene diamines can also be used. Such polyamines can bemade by reacting the above-described alkylene amines with one or more ofthe above-described alkylene oxides. Similar alkylene oxide-alkanolamine reaction products may also be used such as the products made byreacting the above described primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a 1.1 to 1.2 molarratio. Reactant ratios and temperatures for carrying out such reactionsare known to those skilled in the art. Specific examples ofhydroxy-containing polyamines include N-(2-hydroxyethyl)ethylenedianminie, N,N′-bis(2-hydroxyethyl)-ethylenediamine,1-(2-hydroxyethyl)-piperazine, mono(hydroxypropyl)-substitutedtetraethylenepentamine. N-(3-hydroxybutyl)-tetramethylene diamine, etc.Higher homologs obtained by condensation of the above illustratedhydroxy-containing polyamines through amino groups or through hydroxygroups are likewise useful. Condensation through amino groups results ina higher amine accompanied by removal of ammonia while condensationthrough the hydroxy groups results in products containing ether linkagesaccompanied by removal of water. Mixtures of two or more of any of theabove described polyamines are also useful.

[0149] In another embodiment, the amine is a heterocyclic amine Theheterocyclic polyamincs include aziridines, azetidines, azolidines,tetra- and dihydropyridines, pyrroles, indoles, piperidines, imidazoles,di- and tetrahydroimidazoles, piperazines, isoindoles, purines,morpholines, thiomorpholines, N-aminoalkylmorpholines.N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,N,N′-di-aminoalkylpiperazines, azepines, azocines, azonines, azecinesand tetra-, di- and per-hydro derivatives of each of the above andmixtures of two or more of these heterocyclic amines. Preferredheterocyclic amines are the saturated 5- and 6-membered heterocyclicamines containing only nitrogen, oxygen and/or sulfur in the heteroring, especially the piperidines, piperazines, thiomorpholines,morpholines, pyrrolidines, and the like. Piperidine, aminoalkylsubstituted piperidines, piperazine, aminoalkyl substituted piperazines,morpholine, aminoalkyl substituted morpholines, pyrrolidine, andaminoalkyl-substituted pyrrolidines, are especially preferred. Usuallythe aminoalkyl substituents are substituted on a nitrogen atom formingpart of the hetero ring. Specific examples of such heterocyclic aminesinclude N-aminopropylmorpholine, N-aminoethylpiperazine, andN,N′-diaminoethylpiperazine. Hydroxy heterocyclic amines are alsouseful. Examples include N-(2-hydroxyethyl)cyclohexylamine,3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethylpiperazine,and the like.

[0150] The metal salts of the phosphorus acid esters are prepared by thereaction of a metal base with the phosphorus acid ester. The metal basemay be any metal compound capable of forming a metal salt. Examples ofmetal bases include metal oxides, hydroxides, carbonates, sulfates,borates, or the like. The metals of the metal base include Group IA,IIA, IB through VIIB, and VIII metals (CAS version of the Periodic Tableof the Elements). These metals include the alkali metals, alkaline earthmetals and transition metals. In one embodiment, the metal is a GroupIIA metal, such as calcium or magnesium, Group IIB metal, such as zinc,or a Group VIIB metal, such as manganese. Preferably the metal ismagnesium, calcium. mnanganese or zinc Examples of metal compounds whichmay be reacted with the phosphorus acid include zinc hydroxide, zincoxide, copper hydroxide, copper oxide, etc.

[0151] In one embodiment, phosphorus or boron containingantiwear/extreme pressure agent is a metal thiophosphate, preferably ametal dithiophosphate. The metal thiophosphate is prepared by meansknown to those in the art. Examples of metal dithiophosphates includezinc isopropyl, methylamyl dithiophosphate, zinc isopropyl isooctyldithiophosphate, barium di(nonyl) dithiophosphate, zinc di(cyclohexyl)dithiophosphate, zinc di(isobutyl) dithiophosphate, calcium di(hexyl)dithiophosphate, zinc isobutyl isoamyl dithiophosphate, and zincisopropyl secondary-butyl dithiophosphate.

[0152] The following Examples P-3 to P-6 exemplify the preparation ofuseful phosphorus acid ester salts.

EXAMPLE P-3

[0153] A reaction vessel is charged with 217 grams of the filtrate fromExample P-1. A commercial aliphatic primary amine (66 grams), having anaverage molecular weight of 191 in which the aliphatic radical is amixture of tertiary alkyl radicals containing from 11 to 14 carbon atom,is added over a period of 20 minutes at 25-60° C. The resulting producthas a phosphorus content of 10.2% by weight, a nitrogen content of 1.5%by weight, and an acid number of 26.3.

EXAMPLE P-4

[0154] Following the procedures of Examples P-1 and P-3, 1320 parts ofthe product described in P-1 was reacted with 584 parts of the amine ofP-3. The final product has 8.4% phosphorus and 10% sulfur.

EXAMPLE P-5

[0155] The filtrate of Example P-2 (1752 grams) is mixed at 25-82° C.with 764 grams of the aliphatic primary amine used in of Example P-3 Theresulting product has 9.9% phosphorus, 2.7% nitrogen, and 12.6% sulfur.

EXAMPLE P-6

[0156] Phosphorus pentoxide (852 grams) is added to 2340 grams ofiso-octyl alcohol over a period of 3 hours. The temperature increasesfrom room temperature but is maintained below 65° C. After the additionis complete the reaction mixture is heated to 90° C. and the temperatureis maintained for 3 hours. Diatomaceous earth is added to the mixture,and the mixture is filtered. The filtrate has 12.4% phosphorus, a 192acid neutralization number (bromophenol blue) and a 290 acidneutralization number (phenolphthalein).

[0157] The above filtrate is mixed with 200 grams of toluene, 130 gramsof mineral oil, 1 gram of acetic acid, 10 grams of water and 45 grams ofzinc oxide. The mixture is heated to 60-70° C. under a pressure of 30 mmHg. The resulting product mixture is filtered using a diatomaceousearth. The filtrate has 8.6% zinc and 7.0% phosphorus.

EXAMPLE P-7

[0158] Alfol 8-10 (2628 parts, 18 moles) is heated to a temperature ofabout 45° C. whereupon 852 parts (6 moles) of phosphorus pentoxide areadded over a period of 45 minutes while maintaining the reactiontemperature between about 45-65° C. The mixture is stirred an additional0.5 hour at this temperature, and is there- after heated at 70° C. forabout 2-3 hours. Primene 81-R (2362 parts, 12.6 moles) is added dropwiseto the reaction mixture while maintaining the temperature between about30-50° C. When all of the amine has been added, the reaction mixture isfiltered through a filter aid, and the filtrate is the desired aminesalt containing 7.4% phosphorus (theory, 7.1%).

EXAMPLE P-8

[0159] Phosphorus pentoxide (208 grams) is added to the product preparedby reacting 280 grams of propylene oxide with 1184 grams ofO,O′-di-isobutylphosphorodithioic acid at 30-60° C. The addition is madeat a temperature of 50-60° C. and the resulting mixture is then heatedto 80° C. and held at that temperature for 2 hours The commercialaliphatic primary amine identified in Example P-3 (384 grams) is addedto the mixture, while the temperature is maintained in the range of30-60° C. The reaction mixture is filtered through diatomaceous earth.The filtrate has 9.3% phosphorus, 11.4% sulfur, 2.5% nitrogen, and abase number of 6.9 (bromophenol blue indicator).

[0160] In another embodiment, the phosphorus or boron antiwear/extremepressure agent is a metal salt of (a) at least one dithiophosphoric acidand (b) at least one aliphatic or alicyclic carboxylic acid. Thedithiophosphoric acids are described above. The carboxylic acid may be amonocarboxylic or polycarboxylic acid, usually containing from 1 toabout 3, or just one carboxylic acid group. The preferred carboxylicacids are those having the formula RCOOH, wherein R is an aliphatic oralicyclic hydrocarbyl group preferably free from acetylenicunsaturation. R generally contains from about 2, or from about 4 carbonatoms. R generally contains up to about 40, or up to about 24, or to upabout 12 carbon atoms. In one embodiment, contains from 4, or from about6 up to about 12, or up to about 8 carbon atoms. In one embodiment, R isan alkyl group. Suitable acids include the butanoic, pentanoic,hexanoic, octanoic, nonanoic, decanoic, dodecanoic, octodecanoic andeicosanoic acids, as well as olefinic acids such as oleic, linoleic, andlinolenic acids and linoleic acid dimer. A preferred carboxytic acid is2-ethylhexanoic acid.

[0161] The metal salts may be prepared by merely blending a metal saltof a dithiophoshoric acid with a metal salt of a carboxylic acid in thedesired ratio. The ratio of equivalents of dithiophosphoric acid tocarboxylic acid is from about 0.5 up to about 400 to 1. The ratio may befrom 0.5 up to about 200, or up to about 100, or up to about 50, or upto about 20 to 1. In one embodiment, the ratio is from 0.5 up to about4.5 to one, preferably from about 2.5 up to about 4.25 to one. For thispurpose, the equivalent weight of a dithiophosphoric acid is itsmolecular weight divided by the number of -PSSH groups therein, and theequivalent weight of a carboxylic acid is its molecular weight dividedby tire number of carboxy groups therein.

[0162] A second and preferred method for preparing the metal saltsuseful in this invention is to prepare a mixture of the acids in thedesired ratio, such as those described above for the metal salts of theindividual metal salts, and to react the acid mixture with one of theabove described metal compounds. When this method of preparation isused, it is frequently possible to prepare a salt containing an excessof metal with respect to the number of equivalents of acid present; thusthe metal salts may contain as many as 2 equivalents and especially upto about 1.5 equivalents of metal per equivalent of acid may beprepared, the equivalent of a metal for this purpose is its atomicweight divided by its valence. The temperature at which the metal saltsare prepared is generally between about 30° C. and about 150° C.,preferably up to about 125° C. U.S. Pat. Nos. 4,308,154 and 4,417,990describe procedures for preparing these metal salts and disclose anumber of examples of such metal salts. These patents are herebyincorporated by reference for those disclosures.

[0163] In one embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is a phosphorus containing amide. Thephosphorus containing amides are prepared by the reaction of one of theabove describe phosphorus acids, preferably a dithiophosphoric acid,with an one of the above described unsaturated amides. The reactionproduct of the phosphorus acid and the unsaturated amide may be furtherreacted with a linking or a coupling compound, such as formaldehyde orparaformaldehyde. The phosphorus containing amides are known in the artand are disclosed in U.S. Pat. Nos. 4,670,169, 4,770,807, and 4,876,374which are incorporated by reference for their disclosures of phosphorusamides and their preparation.

[0164] In one embodiment, the phosphorus or boron antiwear/extremepressure agent is a phosphorus containing carboxylic ester. Thephosphorus containing carboxylic esters are prepared by reaction of oneof the above-described phosphorus acids, preferably a dithiophosphoricacid, and one of the above described unsaturated carboxylic acids oresters. If the carboxylic acid is used, the ester may then be formed bysubsequent reaction of the phosphoric acid-unsaturated carboxylic acidadduct with an alcohol, such as those described herein.

[0165] In one embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is a reaction product of a phosphorusacid, preferably a dithiophosphoric acid, and one of the above describedvinyl ethers.

[0166] In another embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is an alkali metal borate. Alkali metalberates are generally a hydrated particulate alkali metal borate whichare known in the art. Alkali metal borates include mixed alkali andalkaline earth metal borates. These alkali metal borates are availablecommercially. Representative patents disclosing suitable alkali metalborates and their methods of manufacture include U.S. Pat. Nos.3,997,454; 3,819,521; 3,853,772; 3,907,601; 3,997,454; and 4,089,790.These patents are incorporated by reference for their disclosures ofalkali metal borates and methods of their manufacture.

[0167] In another embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is a borated overbased compound,provided that the borated overbased compound is different than B(i)above. The borated overbased compounds are described above.

[0168] In another embodiment, the phosphorus or boron antiwear/extremepressure agent is a borated fatty amine. The borated amines are preparedby reacting one or more of the above boron compounds, such as boricacid, with one or more of the above fatty amines, e.g. an amine havingfrom about four to about eighteen carbon atoms. The borated fatty aminesare prepared by reacting the amine with the boron compound at about 50°C. to about 300° C., preferably about 100° C. to about 250° C., and at aratio of 3:1 to 1:3 equivalents of amine to equivalents of boroncompound.

[0169] In another embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is a borated epoxide. The borated fattyepoxides are generally the reaction product of one or more of the aboveboron compounds, with at least one epoxide. The epoxide is generally analiphatic epoxide having at least 8, preferably about 10, morepreferably about 12, up to about 24, preferably 20 carbon atoms.Examples of useful aliphatic epoxides include heptyl oxide, octyl oxide,stearyl oxide, oleyl oxide and the like. Mixtures of epoxides may alsobe used, for instance commercial mixtures of epoxides having from 14 toabout 16 carbon atoms and from 14 to about 18 carbon atoms. The boratedfatty epoxides are generally known and are disclosed in U.S. Pat. No.4,584,115. This patent is incorporated by reference for its disclosureof borated fatty epoxides and methods for preparing the same.

[0170] In another embodiment, the phosphorus or boron containingantiwear/extreme pressure agent is a borated phospholipid. The beratedphospholipids are prepared by reacting a combination of a phospholipidand a boron compound. Optionally, the combination may include an amine,an acylated nitrogen compound, such as reaction products of carboxylicacylating agents and polyamines, a carboxylic ester, such as reactionproducts of carboxylic acrylating agents and alcohols and optionallyamines, a Mannich reaction product, or a basic or neutral metal salt ofan organic acid compound. Phospholipids, sometimes referred to asphosphatides and phospholipins, may be natural or synthetic. Naturallyderived phospholipids include those derived from fish, fish oil,shellfish, bovine brain, chicken eggs, sunflowers, soybean, corn, andcottonseed. Phospholipids may be derived from microorganisms, includingblue-green algae, green algae, and bacteria.

[0171] The reaction of the phospholipid, the boron compound, and theoptional components usually occurs at a temperature from about 60° C. toabout 200° C., or from about 90° C. up to about 150° C. The reaction istypically accomplished in about 0.5, or about 2 up to about 10 hours.The boron compound and phospholipid are reacted at an atomic proportionratio of boron to phosphorus from about one up to about six to one,preferably from about two up to about four to one, more preferably aboutthree to one. When the combination includes additional components, theboron compound is reacted with the mixture of the phospholipid and oneor more optional ingredients in an amount of one atomic proportion ofboron to an equivalent of the mixture of a phospholipid and an optionalingredient in a ratio from about (1:1), up to about (6:1), or from about(2:1) up to about (4:1). The equivalents of the mixture are based on thecombined equivalents of phospholipid based on phosphorus and equivalentsof the optional ingredients. The borated phospholipids are described inEuropean publication EP 540,700. This publication is incorporated byreference.

[0172] In another embodiment, the molybdenum containing compositions maybe used in combination with a mixture of (i) a borated overbasedcomposition and (ii) an organic polysulfide or an ashlessdithiocarbamate containing composition and a phosphorus or boronantiwear/extreme pressure agent. These components are described above.

[0173] Lubricants

[0174] As previously indicated, the above combinations are useful inlubricants where they can function primarily as antiwear, antiweld,extreme pressure, anticorrosion antioxidation and/or friction modifyingagents. They can be employed in a variety of lubricants based on diverseoils of lubricating viscosity, including natural and syntheticlubricating oils and mixtures thereof. These lubricants includecrankcase lubricating oils for spark-ignited and compression-ignitedinternal combustion engines, including automobile and truck engines,two-cycle engines, aviation piston engines, marine and railroad dieselengines, and the like. They can also be used in gas engines, stationarypower engines and turbines and the like. Automatic or manualtransmission fluids, transaxle lubricants, gear lubricants, includingopen and enclosed gear lubricants, tractor lubricants, metal-workinglubricants, hydraulic fluids and other lubricating oil and greasecompositions can also benefit from the incorporation therein of thecompositions of the present invention. They may also be used aswirerope, walking cam, way, rock drill, chain and conveyor belt, wormgear, bearing, and rail and flange lubricants.

[0175] The combinations may be used in lubricants or in concentrates.The concentrate may contain the above combinations and/or othercomponents used in preparing fully formulated lubricants. Theconcentrate also contains a substantially inert organic diluent, whichincludes kerosene, mineral distillates, or one or more of the oils oflubricating viscosity discussed below. The combinations are present in afinal product, blend, or concentrate in any amount effective to act asan antiwear, antiweld, and/or extreme pressure agents in lubricatingcompositions.

[0176] In one embodiment, the lubricating composition contains up to1.5%, or up to about 1.0%, or up to about 0.5% by weight of reactionproduct of a polyisobutenyl substituted succinic anhydride and apolyalkylene polyamine. In another embodiment, the lubricatingcompositions, such as gear lubricants, contain up to 2%, or up to 1.5%,or up to 1% by weight of a dispersant, such as those described herein.In another embodiment, the lubricating composition is free of added leadcompounds, such as lead napthanates, dithiophosphates anddithiocarbamates.

[0177] The lubricating compositions and methods of this invention employan oil of lubricating viscosity, including natural or syntheticlubricating oils and mixtures thereof. Natural oils include animal oils,vegetable oils, mineral lubricating oils, and solvent or acid treatedmineral oils. Synthetic lubricating oils include hydrocarbon oils(polyalpha-olefins), halo-substituted hydrocarbon oils, alkylene oxidepolymers. esters of dicarboxylic acids and polyols, esters ofphosphorus-containing acids, polymeric tetrahydrofurans andsilicon-based oils. Unrefined, refined, and rerefined oils, eithernatural or synthetic, may be used in the compositions of the presentinvention. A description of oils of lubricating viscosity occurs in U.S.Pat. No. 4,582,618 (column 2, line 37 through column 3, line 63,inclusive), herein incorporated by reference for its disclosure to oilsof lubricating viscosity.

[0178] In one embodiment, the oil of lubricating viscosity is apolyalpha-olefin (PAO). Typically, the polyalpha-olefins are derivedfrom monomers having from about 3 to about 30, or from about 4 to about20, or from about 6 to about 16 carbon atoms. Examples of useful PAOsinclude those derived from decene. These PAOs may have a viscosity fromabout 3 to about 150, or from about 4 to about 100, or from about 4 toabout 8 cSt at 100° C. Examples of PAOs include 4 cSt polyolefins, 6 cStpolyolefins, 40 cSt polyolefins and 100 cSt polyalphaolefins.

[0179] In one embodiment, the oil of lubricating viscosity are selectedto provide lubricating compositions with a kinematic viscosity of atleast about 3.5 cSt, or at least about 4.0 cSt at 100° C. In oneembodiment, the lubricating compositions have an SAE gear viscositygrade of at least about SAE 75W. The lubricating composition may alsohave a so-called multigrade rating such as SAE 75W-80, 75W-90, 75W-90,75W-140, 80W-90, 80W-140, 85W-90, or 85W-140. Multigrade lubricants mayinclude a viscosity improver which formulated with the oil oflubricating viscosity to provide the above lubricant grades. Usefulviscosity improvers include but are not limited to polyolefins, such asethylene-propylene copolymers, or polybutylene rubbers, includinghydrogenated rubbers, such as styrene-butadiene or styrene-isoprenerubbers; or polyacrylates, including polymethacrylates. In oneembodiment, the viscosity improver is a polyolefin or polymethacrylate.Viscosity improvers available commercially include Acryloid™ viscosityimprovers available from Rohm & Haas; Shellvis™ rubbers available fromShell Chemical; Trilene™ polymers, such as Trilene™ CP-40, availablecommercially from Uniroyal Chemical Co., and Lubrizol 3100 series and8400 series polymers, such as Lubrizol 3174 available from The LubrizolCorporation.

[0180] In one embodiment, the oil of lubricating viscosity includes atleast one ester of a dicarboxylic acid. Typically the esters containingfrom about 4 to about 30, preferably from about 6 to about 24, or fromabout 7 to about 18 carbon atoms in e each ester group. Examples ofdicarboxylic acids include glutaric, adipic, pimelic, suberic, azelaicand sebacic. Examples of ester groups include hexyl, octyl, decyl, anddodecyl ester groups. The ester groups include linear as well asbranched ester groups such as iso arrangements of the ester group. Aparticularly useful ester of a dicarboxylic acid is diisodecyl azelate.

[0181] In another embodiment, the oil of lubricating viscosity isselected to provide lubricating compositions for crankcase applications,such as for gasoline and diesel engines Typically, the lubricatingcompositions are selected to provide an SAE crankcase viscosity numberof 10W, 20W, or 30W lubricants. The lubricating composition may alsohave a so called multi-grade rating such as SAE 5W-30, 10W-30, 10W-40,20W-50, etc. As described above, multi-grade lubricants include aviscosity improver which is formulated with the oil of lubricatingviscosity to provide the above lubricant grades.

[0182] Other Additives

[0183] The invention also contemplates the use of other additivestogether with the above combinations Such additives include, forexample, detergents and dispersants. corrosion- and oxidation-inhibitingagents, pour point depressing agents, extreme pressure agents, antiwearagents, color stabilizers and anti-foam agents.

[0184] The detergents are exemplified by oil-soluble neutral and basicsalts (i.e. overbased salts) of alkali or alkaline earth metals withsulfonic acids, carboxylic acids, phenols or organic phosphorus acids,such as those described above. The oil-soluble neutral or basic salts ofalkali or alkaline earth metal salts may also be reacted with a boroncompound. Boron compounds are described above. The overbased and boratedoverbased metal salts are described above. Examples of useful overbasedand borated overbased metal salts include sodium, calcium and magnesiumoverbased and borated overbased sulfonates and carboxylates, includingthe above hydrocarbyl substituted carboxylic acylating agents.

[0185] Detergents and dispersants are known in the art. The followingare illustrative.

[0186] (1) “Carboxylic dispersants,” are the reaction products ofcarboxylic acids (or derivatives thereof) containing at least about 34and preferably at least about 54 carbon atoms and nitrogen containingcompounds (such as amines), organic hydroxy compounds (such as phenolsand alcohols), and/or basic inorganic materials. These reaction productsinclude imide, amide, and ester reaction products of carboxylicacylating agents. The carboxylic dispersants are generally prepared byreacting one or more of the above described hydrocarbyl substitutedcarboxylic acylating agent (described above) with an amine (describedabove), preferably the polyalkylenepolyamine or the condensed polyamine,or hydroxy containing compound, such as an alcohol and optionally anamine. Examples of these materials include succinimide dispersants andcarboxylic ester dispersants. Examples of these “carboxylic dispersants”are described in British Patent 1,306,529 and in many U.S. patentsincluding the following: U.S. Pat. Nos. 3,219,666, 3,316,177, 3,340,281,3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405,3,542,680, 3,576,743, 3,632,511, 4,234,435, 5,230,714 and Re 26,433.

[0187] (2) “Amine dispersants” are the reaction products of relativelyhigh molecular weight aliphatic or alicyclic halides and amines,preferably polyalkylene polyamines. These dispersants are describedabove as polyalkene-substituted amines. Examples thereof are describedfor example, in the following U.S. Pat. Nos. 3,275,554, 3,438,757,3,454,555, and 3,565,804.

[0188] (3) “Mannich dispersants” are the reaction products ofalkylphenols anti aldehydes (especially formaldehyde) and amines(especially amine condensates and polyalkylenepolyamines). The materialsdescribed in the following U.S. patents are illustrative: U.S. Pat. Nos.3,036,003, 3,236,770, 3,414,347, 3,448,047, 3,461,172, 3,539,633.3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882, and 3,980,569.

[0189] (4) “Post-treated dispersants” are the products obtained bypost-treating the carboxylic, amine or Mannich dispersants with reagentssuch as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylicacids, hydrocarbon-substituted succinic anhydrides, nitrites, epoxides,boron compounds, phosphorus compounds or the like. Exemplary materialsof this kind are described in the following U.S. Pat. Nos. 3,200,107,3,282,955, 3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808,3,455,832, 3,579,450, 3,600,372, 3,702,757,and 3,708,422.

[0190] (5) “Polymeric dispersants” are interpolymers of oil-solubilizingmonomers such as decyl methacrylate, vinyl decyl ether and highmolecular weight olefins with monomers containing polar substituents,e.g., aminoalkyl acrylates or acrylamides andpoly-(oxyethylene)-substituted acrylates. Polymeric dispersants includeesters of styrene-maleic anhydride copolymers. Examples thereof aredisclosed in the following U.S. Pat. Nos. 3,329,658, 3,449,250,3,519,656, 3,666,730, 3,687,849, and 3,702,300.

[0191] The above-noted patents are incorporated by reference herein fortheir disclosures of ashless dispersants.

[0192] Auxiliary extreme pressure agents and corrosion- andoxidation-inhibiting agents which may be included in the lubricants ofthe invention are exemplified by chlorinated aliphatic hydrocarbons suchas chlorinated waxes; sulfurized alkylphenols; phosphites including di-or trihydrocarbyl phosphites, such as dibutyl phosphite, trioleylphosphite and triphenyl phosphite; phosphosulfurized hydrocarbons, suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate; metal thiocarbamates, such as zincdioctyldithiocarbamate, and barium diheptylphenyl dithiocarbamate. Manyof the above-mentioned extreme pressure agents and corrosion- andoxidation-inhibitors also serve as antiwear agents.

[0193] Pour point depressants are an additive often included in thelubricating oils described herein. Examples of useful pour pointdepressants are polymethacrylates; polyacrylates; polyacrylamides:condensation products of haloparaffin waxes and aromatic compounds;vinyl carboxylate polymers; and polymers of dialkylfumarates, vinylesters of fatty acids and alkyl vinyl ethers. Pour point depressantsuseful for the purposes of this invention, techniques for theirpreparation and their uses are described in U.S. Pat. Nos. 2,387,501;2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877;2,721,878; and 3,250,715 which are hereby incorporated by reference fortheir relevant disclosures.

[0194] Antifoam agents are used to reduce or prevent the formation ofstable foam. Typical antifoam agents include silicones or organicpolymers. Additional antifoam compositions are described in “FoamControl Agents”, by Henry T. Kerner (Noyes Data Corporation, 1976),pages 125-162.

[0195] The following examples relate to lubricating compositionscontaining the combination of a dithiocarbamate compound and an organicpolysulfide.

[0196] EXAMPLE 1

[0197] A lubricant is prepared by incorporating 1.5% by weight of theproduct of Example M-1 and 1% of the product of Example B-2 into a80W-90 gear oil base oil.

EXAMPLE 2

[0198] A lubricating composition is prepared as described in Example 1,except a 10W-30 oil is used instead of the 80W-90 oil.

EXAMPLE 3

[0199] A lubricating oil is prepared by incorporating 1.5% of theproduct of Example M-1, 2.5% of the product of Example S-1, and 1.2% byweight of the product of Example P-3 into an 80W-90 gear oil.

EXAMPLE 4

[0200] A lubricating composition is prepared as described in Example 3except a 10W-30 oil is used instead of the 80W-90 oil.

EXAMPLE 5

[0201] A lubricating oil is prepared by incorporating 1.5% of theproduct of Example M-1, 1% of the product of Example B-2, 2.5% of theproduct of Example S-1, 1.2% of a mixed salt of isooctyldithiophosphoric acid and 2-ethylhexanoic acid, 0.7% of dibutyl hydrogenphosphite, 1.8% of calcium overbased salt of an alkylbenzene sulfonicacid (having a metal ratio of 12, 53% diluent, comprising 100 neutralmineral oil and unreacted alkylbenzene alkylate, a total base number of30, and a 385 molecular weight for the sulfonic acid), 0.25% ofoleylamide, and 0.07% of silicon antifoam agent into a 80W-90 oil.

EXAMPLE 6

[0202] A lubricating compositions is prepared by incorporating 0.2% byweight of Sakura Lube 500, 3.8% by weight to the product of Example S-1,1.3% by weight of the product of Example P-3.

EXAMPLE 7

[0203] The lubricating composition is prepared by incorporating 0.2% ofSakura Lube 500, 3.8% by weight of the product of Example S-1, 1.3% byweight of the product of Example P-4, 0.35% by weight of oleo amine,0.1% by weight oleo amide, and 0.1% by weight of the reaction product ofdimercaptothiadiazole, heptylamine and paraformaldehyde into an 80W gearoil.

EXAMPLE 8-12

[0204] The following table contains examples of lubricating compositionswhich are prepared by incorporating the ingredients into an 80W-90 gearoil. 6 7 8 9 10 11 Example M-1 1.5 — — 2.5 1.0 — Sakura Lube 500 — 0.2 —— — 0.3 Molyvan 807 — — 0.5 — — — Example B-1 1 — — 1.5 — 0.5 ExampleB-2 — 0.8 — — 1 0.8 Example S-1 3.0 — 2.5 — — 3.0 Example P-4 — — 1.2 —— — Example P-4 1.2 — — 1.2 1.2 — Phosphorus — 1.5 — — — 1.5 Containingester¹ Dithiocarbamate — 2.5 1 — 2.5 — ester² Dibutyl hydrogen 0.7 — — —— 1.0 phosphite

[0205] While the invention has been explained in relation to itspreferred embodiments, it is to be understood that various modificationsthereof will become apparent to those skilled in the art upon readingthe specification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

1. A lubricating composition comprising a major amount of an oil oflubricating viscosity and (A) an antiwear improving amount of at leastone molybdenum containing composition, and (B) at least one memberselected from the group consisting of (i) at least one borated overbasedmetal salt of an acidic organic compound, provided that (A) and (Bi) arenot the same, (ii) a combination of (a) at least one organic polysulfideor at least one ashless dithiocarbamate containing composition and (b)at least one component selected from the group consisting of a metalthiophosphate, a phosphoric acid ester or salt thereof, aphosphorus-containing carboxylic acid, ester, ether, or amide, a borateddispersant, an alkali metal borate, a borated fatty amine, a boratedphospholipid, a borate ester, and mixtures thereof, and (iii) acombination of (i) and (ii).
 2. The composition of claim 1, wherein (A)is present in an amount to provide from about 125 to about 900 ppmmolybdenum to the lubricating composition.
 3. The composition of claim1, wherein (A) is a molybdenum containing alkali or alkaline earth metaloverbased sulfonate, carboxylate, or phenate.
 4. The composition ofclaim 1, wherein (A) is molybdenum containing alkali or alkaline earthmetal sulfonate.
 5. The composition of claim 4, wherein the alkaline oralkaline earth metal is calcium or magnesium.
 6. The composition ofclaim 1 wherein (A) is prepared by carbonation of a mixture comprisingat least one alkali or alkaline earth metal compound, an acidic organiccompound, and at least one hydrocarbon insoluble organic molybdenumcomplex.
 7. The composition of claim 6 wherein the organic molybdenumcomplex is an amine molybdenum complex.
 8. The composition of claim 1wherein (A) is at least one molybdenum thiophosphate or at least onemolybdenum thiocarbamate.
 9. The composition of claim 1 wherein (A) isat least one molybdenum oxysulfide dithiophosphate or at least onemolybdenum oxysulfide dithiocarbamate.
 10. The composition of claim 1,wherein (B) is (i) and the borated overbased salt of an acidic organiccompound is a borated overbased alkali or alkaline earth metalsulfonate, carboxylate or phenate.
 11. The composition of claim 1wherein (B) is (i) and the borated overbased salt of an acidic organiccompound is a borated overbased sodium, calcium or magnesium sulfonateor carboxylate.
 12. The composition of claim 1, wherein (B) is (i) andthe lubricating composition further comprises (C) at least onesulfurized organic compound or at least one ashless dithiocarbamatecontaining compound, or (D) at least one phosphorus or boron extremepressure.
 13. The composition of claim 1 wherein (B) is (ii) and theorganic polysulfide is a sulfurized oil, fatty acid or ester, olefin,polyolefin or mixtures thereof.
 14. The composition of claim 1 wherein(B) is (ii) and the ashless dithiocarbamate containing composition (a)is prepared by reacting a dithiocarbamic acid or salt with anunsaturated compound.
 15. The composition of claim 14 wherein theunsaturated compound is an acrylic ester of the formulaR¹R²C═C(R³)COOR⁴, wherein R¹, R², and R³ are each independently hydrogenor a hydrocarbyl group, and R⁴ is a hydrocarbyl group containing from 1to about 24 carbon atoms.
 16. The composition of claim 14 wherein theunsaturated compound is a methyl, ethyl, butyl, pentyl, orhexyl-acrylate or methacrylate.
 17. The composition of claim 1 whereinthe phosphoric acid ester or salt thereof (b) is a phosphoric acid esterprepared by reacting a dithiophosphoric acid with an epoxide to form anintermediate, and the intermediate is further reacted with a phosphorusacid or anhydride, or a salt of the phosphoric acid ester.
 18. Thecomposition of claim 17 wherein the dithiophosphoric acid is adihydrocarbyl dithiophosphoric acid independently having from 1 to about24 carbon atoms in each hydrocarbyl group.
 19. The composition of claim18 wherein the phosphoric acid ester or salt thereof is prepared byreacting the phosphoric acid ester with ammonia or an amine.
 20. Thecomposition of claim 19 wherein the amine is a tertiary aliphaticprimary amine.
 21. The composition of claim 1 wherein the phosphoricacid ester or salt thereof (b) is a phosphoric acid ester prepared byreacting a phosphorus acid or anhydride with at least one alcoholwherein each alcohol independently contains from about 1 to about 30carbon atoms, or a salt of the phosphoric acid ester.
 22. Thecomposition of claim 1 wherein the phosphoric acid ester or salt thereofis a triarylphosphate.
 23. The composition of claim 22 wherein thetriarylphosphate is tricresylphosphate.
 24. The composition of claim 12,wherein (C) is a sulfurized olefin.
 25. A lubricating compositioncomprising a major amount of an oil of lubricating viscosity and (A) anantiwear improving amount of at least one molybdenum containingcomposition, and (B) at least one borated overbased metal salt of anacidic organic compound, provided that (A) and (B) are not the same. 26.The composition of claim 25, wherein (A) is present in an amount toprovide from about 125 to about 900 ppm molybdenum to the lubricatingcomposition.
 27. The composition of claim 25, wherein (A) is amolybdenum containing alkali or alkaline earth metal overbasedsulfonate, carboxylate, or phenate.
 28. The composition of claim 25,wherein (A) is a molybdenum containing alkali or alkaline earth metaloverbased sulfonate.
 29. The composition of claim 25 wherein (A) isprepared by carbonation of a mixture comprising at least one alkali oralkaline earth metal compound, an acidic organic compound, and at leastone hydrocarbon insoluble organic molybdenum complex.
 30. Thecomposition of claim 29 wherein the organic molybdenum complex is anamine molybdenum complex.
 31. The composition of claim 25 wherein (A) isa molybdenum thiophosphate or a molybdenum thiocarbamate.
 32. Thecomposition of claim 25 wherein (A) is a molybdenum oxysulfidedithiophosphate or a molybdenum oxysulfide dithiocarbamate.
 33. Thecomposition of claim 25, wherein (B) the borated overbased salt of anacidic organic compound is a borated overbased alkali or alkaline earthmetal sulfonate, carboxylate or phenate.
 34. The composition of claim 25A herein (B) is a borated overbased sodium, calcium, or magnesiumsulfonate or carboxylate.
 35. The composition of claim 25, furthercomprises (C) at least one organic polysulfide or at least onedithiocarbamate containing compound, or (D) at least one phosphorus orboron antiwear or extreme pressure, wherein (B) and (D) are not thesame.
 36. The composition of claim 35, wherein (C) is a sulfurizedolefin.
 37. The composition of claim 35, wherein (C) is adithiocarbamate ester prepared by reacting a dithiocarbamic acid or saltwith an unsaturated compound.
 38. A lubricating composition comprising amajor amount of an oil of lubricating viscosity, (A) at least onemolybdenum containing composition, and (B) at least one combination of(a) at least one organic polysulfide or at least one ashlessdithiocarbamate containing composition and (b) a component selected fromthe group consisting of a metal thiophosphate, a phosphoric acid esteror salt thereof, a phosphorus-containing carboxylic acid, ester, ether,or amide, a borated dispersant, an alkali metal borate, a borated fattyamine, a borated phospholipid, a borate ester, and mixtures thereof. 39.The composition of claim 38, wherein (A) is a molybdenum containingalkali or alkaline earth metal sulfonate.
 40. The composition of claim38 wherein (A) is a molybdenum thiophosphate or a molybdenumthiocarbamate.
 41. The composition of claim 38 wherein (A) is amolybdenum oxysulfide dithiophosphate or a molybdenum oxysulfidedithiocarbamate.
 42. A method of lubricating a transmission or adifferential comprising the steps of introducing to a transmission ordifferential a lubricating composition comprising a major amount of anoil of lubricating viscosity and (A) an antiwear improving amount of atleast molybdenum containing composition, and (B) at least one memberselected from the group consisting of (i) at least one borated overbasedmetal salt of an acidic organic compound, provided that (A) and (Bii)are not the same, (ii) a combination of (a) at least one organicpolysulfide or at least one ashless dithiocarbamate containingcomposition and (b) at least one component selected from the groupconsisting of a metal thiophosphate, a phosphoric acid ester or saltthereof, a phosphorus-containing carboxylic acid, ester, ether, oramide, a borated dispersant, an alkali metal borate, a borated fattyamine, a borated phospholipid, a borate ester, and mixtures thereof, and(iii) a combination of (i) and (ii), and operating the differential ortransmission.